ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY STUDY - EVOLUTION MODELING OF CORROSION

PRODUCTS LAYER FORMED AT HOT DIP GALVANIZED REBAR–FRESH CONCRETE INTERFACE

UTILIZAREA SPECTROSCOPIEI DE IMPEDANȚĂ ELECTROCHIMICĂ ÎN SCOPUL CARACTERIZĂRII

STRATULUI DE PRODUȘI DE COROZIUNE FORMAT LA INTERFAȚA ARMATURĂ ZINCATA TERMIC –
BETON PROASPĂT

VASILE RUS1, HORAŢIU VERMEŞAN2*, ANDREEA HEGYI3, ANCUŢA ELENA TIUC2

1 BETAK SA Cluj, Bd. Muncii, nr. 16, Cluj-Napoca, România
2Universitatea Tehnică din Cluj-Napoca, Bd. Muncii, nr. 103-105, Cluj-Napoca, România
3 INCD URBAN-INCERC Sucursala Cluj-Napoca, Calea Florești, nr. 117, Cluj-Napoca, România

Autor corespondent/Corresponding Author, email: horatiu.vermesan@imadd.utcluj.ro, tel. (0741)313529

Abstract
The scope of the paper is to find a model for the evolution of corrosion products formed on hot dip galvanized rebars
in fresh concrete, regarding layer thickness and density. In this study, non-passivated and passivated hot dip
galvanized rebars were used, with various passivation solutions. Tests were performed using Electrochemical
Impedance Spectroscopy (EIS). The corrosion products layer evolution was analyzed using the equivalent circuit
model, best fitted with the EIS experimental plots. The layer evolution model was built by monitoring the layer
thickness variation with time, and based on polarization resistance data.
Experiment results show the formation of two corrosion products layers, one in the rebar vicinity and the other in the
concrete matrix vicinity. The two layers density and resistance evolutions are different; their thickness and density
variations are independent from each other. The presence and effects of hot dip galvanized rebar passivation before
the embedment in fresh concrete, was also emphasized.

Acestă lucrare are drept scop stabilirea unui model de evoluție a grosimii și a densității stratului de produși de
coroziune formați pe armătura zincată termic introdusă în betonul proaspăt. Pentru acest studiu s-au folosit atât
armături zincate termic nepasivate, cât și pasivate, folosind diverse soluții de pasivare pe bază de crom. Pentru
efectuarea testelor experimentale s-a folosit spectroscopia de impedanță electrochimică (EIS). Evoluția stratului de
produși de coroziune s-a studiat luând în considerare parametri circuitului echivalent obținut prin fitarea curbelor de
spectroscopie de impedanță electrochimică obținute experimental. Modelul de evoluție a stratului s-a construit studiind
evoluția în timp a grosimii stratului raportată la rezistența lui la polarizare.
Rezultatele experimentale au indicat formarea a două straturi de produși de coroziune, unul adiacent armăturii și altul
adiacent matricii de beton, a căror densitate și rezistență evoluează diferențiat, prezentând perioade de creștere în
grosime sau de densificare independent unul față de celălalt. De asemenea a fost pusă în evidență influența existenței
și tipului de pasivare aplicat armăturii zincate termic, anterior introducerii acesteia în betonul proaspat.

Key words: Electrochemical Impedance Spectroscopy, hot dip galvanized rebar, corrosion, fresh concrete interface.

1. Introduction
Due to its alkaline content, the concrete protects rebar against corrosion. If the concrete surrounding the rebar is
not properly built, if it is cracked, or too thin, the corrosive agents (water, humidity, air, chemical agents) that enter the
concrete, lead to rebar corrosion initiation [1]. Steel rebar corrosion products have an 8 times higher volume compared
to the uncorroded steel, causing residual stress that leads to concrete cracking and delamination, and ultimately, to
the rebar exposure [1].
Hot dip galvanizing (HDG) is a rebar corrosion protection method used from the beginning of 20th century [2, 3].
However, this method is controversial. Even though the HDG rebars have higher corrosion resistance, some
researchers consider that zinc activation in contact with fresh concrete affects the further behavior of the concrete-
rebar system. In fact, due to the zinc amphoteric quality, HDG rebars react in contact with fresh concrete. Thus, a
small percent of zinc layer is corroded, resulting specific corrosion products and hydrogen evolution [3-11]. The
process stops when the OH- hydroxyl group is consumed as a result of zinc reaction with the solution in concrete
pores, resulting the as-named self-passivation. This leads to pH concrete pores solution decreasing in rebars vicinity,
to safe values, from 11.5 up to 13.2 [12].
HDG rebar passivation before embedment in concrete is a method that reduces zinc reactivity in contact with
fresh concrete. Various passivation methods are described in literature. One of the most accessible methods is to
apply a phosphate layer on the HDG steel rebar. However, the zinc phosphate layer is highly soluble in alkaline
solution and has no positive influence on passive film formation on zinc surface [13]. According to recent studies,
phosphatation using TiO2 nanoparticles in the conversion layer leads to corrosion resistance increase in contact with
fresh concrete [14].
Chromating is a method with much better results. Chromium ions in fresh concrete are oxidation inhibitors that
also are reduced. While chromium ions are reduced, the hydrogen ions aren't reduced to atomic hydrogen. Thus,
gaseous hydrogen does not form [15, 16]. According to Treadaway [17] and Short et al [18], chromating improves
significantly the corrosion resistance, especially under chlorine attack. Also, chromating improves adherence of HDG
rebar to concrete, most likely due to the passivation effect on hydrogen emission reactions [19]. This method
disadvantage however, is the hexavalent chromium toxicity. More environmental friendly passivation methods are
preferred [20, 21].
Cerium salts are considered an environment-friendly alternative to the conversion layers based on Cr (VI).
According to a research presented by Arenas and collaborators, the conversion layers based on cerium ensures an
effective corrosion resistance up to 5 days from embedment and inhibits the hydrogen emission that occur on the
HDG surface during the first hours of contact [22]. Conversion layers based on trivalent chromium, rare earth salts
such as: lanthanum complex salts, cerium salts and vanadium salts [23-25], or based on silanes [26-28] or
molybdenum salts and phosphorus salts [12, 27], are good alternatives to conversion layers based on chromates, due
to their competitive price, low impact on environment, good corrosion resistance and good compatibility with a large
range of substrata.
The purpose of this paper was to study the evolution with time of corrosion products layer thickness/resistance
and density, when non-passivated and passivated HDG rebar in concrete are used, and to find electrochemical
impedance spectroscopy (EIS) parameters. The use of classical, destructive methods of reinforced concrete analysis
would not allow proper information on the formation and evolution of corrosion products layer at the rebar-concrete
interface.

2. Methods and materials used

The corrosion behavior of passivated and of non-passivated HDG rebar in fresh concrete was studied.
Hot-dip galvanization of PC 52 φ 10 mm rebars was performed in industrial conditions, according to all stages of
technological process. An 80 μm zinc coating was obtained.
The HDG rebars were cut in 100 mm samples. For experiments, a part of the samples used were non-passivated
(ZT NP) and the rest were passivated, using various passivation solutions, as shown in Table 1. For obtaining an
effective passivation, the HDG surfaces were activated as follows: lime degreasing, washing, immersion in diluted
sulfuric acid solution for 3 seconds, and washed.
The samples passivation was performed by immersion for 40 seconds in passivation solutions, followed by
washing in running water and drying in hot air flow.
A number of HDG samples were kept non-passivated as reference samples.

Table 1

Subsequent to samples passivation, an active area of 15.7 cm 2 was delimited on the samples surface, while the
remaining samples surface was covered in varnish.
An electrochemical cell was set up for EIS tests, as shown in Figure 1. The electrochemical cell electrodes were
as follows: the working electrode - the passivated or non-passivated HDG rebar, the reference electrode (saturated
Cu/CuSO4 electrode), and the counter-electrode (a graphite rod). The electrolyte was the class C16/20 fresh concrete.
The concrete mixture contained river aggregate with grain size of 0-4 mm, 4-8 mm, and 8-16 mm, cement and water
(with water/cement ratio of 0.65 and the aggregate/cement ratio of 6.61) and a strong water-reducer plasticizer
additive.
Experimental tests were carried out using a potentiostat interfaced with a computer, immediately after electrodes
introduction into the electrolyte (fresh concrete), and then every 12 hours for 2 days. The aim was to monitor the
influence of passivation method on rebar reaction with the strongly alkaline environment of fresh concrete,
immediately after and within 2 days from rebars embedment in concrete. It was assumed that a corrosion products
layer formed at the rebar-concrete interface, with increasing thickness over time, and with uniform density. This layer
was assumed to be constant, typical, influenced only by whether or not the passivation was present and by the
passivation method used.
Figure 2 shows details of the electrochemical cell and electrodes alignment and connection.

Fig. 1 - Schematic representation of the electrochemical cell used to perform electrochemical tests in fresh concrete / Reprezentare
schematică a celulei electrochimice utilizată la realizarea testelor electrochimice în beton proaspăt.

Fig. 2 - Details of electrochemical cell / Detalii ale celulei electrochimice.

 In order not to influence the corrosion products layer thickness, or the double electric layer characteristics, all EIS
tests were conducted in same conditions as follows: a frequency range of f = 100 kHz - 100 MHz and an amplitude of
10 mV, at open circuit potential, and working temperature of 23oC.
Nyquist and Bode experimental plots were interpreted, and fitted based on the equivalent circuit model. Based on
the equivalent circuit components values best fitted to the impedance plots, the concrete pores solution resistance
(Rs), the solution diffusion through the corrosion products layer (Warburg diffusion), and the rebar polarization
resistance (Rp) were found. The system inhomogeneity due to corrosion products layer was compensated by constant
phase CPE capacitive, as shown in Figure 3. The analogy between the physical system and the electrical equivalent
circuit model is shown in Figure 4.

Fig. 3 - Equivalent circuit model used for EIS experimental plots fitting / Circuitul echivalent utilizat la fitarea diagramelor de spectroscopie
de impedanță electrochimică înregistrate experimental.

Fig. 4 - The physical system and equivalent circuit analogy used for impedance plots fitting / Analogia dintre sistemul fizic și circuitul electric
echivalent utilizat la fitarea curbelor de impedanță.

Based on the equivalent circuit components values, the existence of two phases of corrosion products layer was
proposed: a phase formed in the rebar vicinity, with thickness d1; constant phase capacity CPE (CPE-T capacity) and
resistance Rp; and a second phase in the concrete vicinity, with thickness d2 and described by Warburg diffusion
element (with a capacity W-T and a resistance W-R).
Based on the fitting of the impedance plots with the proposed equivalent circuit, the equivalent circuit elements
were calculated, using data recorded immediately after and, 12, 24, 36 and 48 hours after rebar embedment in
concrete:
𝑆𝜀 𝜀
𝐶= 0𝑟 (1)
𝑑
where:
C – capacity; S – surface; ε0 – vacuum permittivity; εr – material relative permittivity; d – layer thickness.
From equation (1):
𝑆 𝜀 𝜀
𝐶𝐶𝑃𝐸−𝑇 = 1 0 𝑟 (2)
𝑑1
𝑆2 𝜀0 𝜀𝑟
𝐶𝑊−𝑇 = (3)
𝑑2
The ratio of the two above capacities gives a relationship between the two corrosion products layers thicknesses:
𝑆1 𝜀0 𝜀𝑟
𝐶𝐶𝑃𝐸−𝑇 𝑑1 𝑑2
= 𝑆2 𝜀0 𝜀𝑟 = (4)
𝐶𝑊−𝑇 𝑑1
𝑑2

Based on data obtained from the equivalent circuit model fitted with impedance plots, the relationship between
thicknesses of the two oxide layer phases was found.
𝐶𝐶𝑃𝐸−𝑇
CCPE-T and CW-T were found from fitting the EIS experimental plots; thus the ratio was found and noted with
𝐶𝑊−𝑇
n1. Equation (4) becomes:
𝑑1 = 𝑛1 𝑑2 (5)
Because Rp and W R can be found from fitting the EIS experimental plots, their ratio is thus known, and is noted
with n2:
𝑅𝑝
= 𝑛2 or 𝑅𝑝 = 𝑛2 𝑊𝑅 (6)
𝑊𝑅
Relating the polarization resistance Rp to the corrosion products layer thickness, replacing it in Equation (6), and
using the d1 value obtained from Equation (5), there result:
𝑅𝑝 𝑛 𝑊 𝑅 𝑛 𝑊
= 2 𝑅 → 𝑝= 2 𝑅 (7)
𝑑1 𝑑1 𝑑1 𝑛1 𝑑2
and
𝑛2 𝑅 𝑊
= 𝑝/ 𝑅 (8)
𝑛1 𝑑1 𝑑2

Finally, based on the equivalent circuit parameters values, the relationship between the corrosion products layer
thickness in the rebar vicinity to the corrosion products layer thickness in the concrete vicinity was found: n1 = d1/d2.
Also, the relationship between thicknesses of the two corrosion products layers and the equivalent circuit parameters
fitted with the EIS plots was found: n2/n1 = (Rp/d1) / (W R/d2).

3. Results and discussions

The aim of the research is to find a relationship for the evolution with time of corrosion products characteristics of
layer formed on rebar after rebar embedment in concrete, and of the parameters found using electrochemical
impedance spectroscopy method (EIS). The corrosion products layer thickness, resistance, were recorded.
The interpretation of EIS experimental plots fitted with the equivalent circuit, lead to the finding of the following
parameters: constant phase element CPE (given by CPE-T), polarization resistance Rp, and the Warburg diffusion
element (W-T capacity and W-R resistance). The n1 and n2 variation parameters and n2/n1 ratio were calculated. The
thickness and density variation of the two corrosion products phases during concrete solidification was found by
analyzing the evolution of the two phases layers thicknesses (n1) and the evolution of the corrosion products layers
resistance relative to their thickness (n2/n1).
The best-fit values of the equivalent circuit components are shown in Table 2.

Table 2

The variation parameters n1 and n2/n1 recorded immediately after and 12, 24, 36 and 48 hours after rebar
embedment in concrete, for the non-passivated galvanized rebar and for the rebars passivated using Permapass or
yellow [CrVI], are shown in Figures 5-7.
The non-passivated HDG rebar (ZT) parameters variation with time is shown in Figure 5a and 5b.
The corrosion products layer is thicker and resistance/thickness ratio is much lower in the rebar vicinity compared
to the corrosion products layer thickness in the concrete vicinity, immediately after rebar embedment in concrete. This
means that in the rebar vicinity a more dense corrosion products layer forms.
Twelve and 24 hours from the rebar embedment in concrete, the corrosion products layer had a
resistance/thickness ratio approx. 2.5 higher in the rebar vicinity compared to the concrete vicinity. This shows the
formation of a dense, highly resistant corrosion products phase in rebar vicinity, while the corrosion products phase in
concrete vicinity is less dense.
This indicates the possibility of two concomitant phenomena: the formation and the migration of the corrosion
products. These phenomena however take place with different speed. The corrosion products migrate into the
concrete after they form. However, the formation rate is lower than the migration rate. Thus, the corrosion products
layer in the rebar vicinity does not densify.
Thirty-six hours after rebar embedment in concrete, the corrosion products phase grows significantly (it becomes
916 times thicker) in the rebar vicinity compared to the concrete vicinity. In the rebar vicinity, the corrosion products
resistance/thickness ratio decreases with time, meaning that the corrosion products layer is less dense during its
growing. Forty-eight hours after rebar embedment in concrete, the layer thickness and density grow, while the
resistance/thickness of corrosion products layer in rebar vicinity becomes 3 times higher compared to the concrete
vicinity. Thus, 36 hours after rebar embedment in concrete, the corrosion products formation rate is high and they
continue to migrate into the concrete matrix. Forty-eight hours after rebar embedment in concrete, the corrosion
products formation rate is still high, and is higher than the migration rate; and thus, the layer density increases in the
rebar vicinity.

(a) (b)
Fig. 5 - Evolution with time of non-passivated HDG rebars for: (a) corrosion products thickness in rebar vicinity and in concrete vicinity ratio
(n1); (b) (Rp·d2)/(Wr·d1) ratio / Evoluția în timp în cazul armăturii zincate termic nepasivată a: (a) raportului dintre grosimea fazei de oxid adiacente
armăturii și grosimea fazei de oxid adiacente betonului (n1); (b) raportului (Rp·d2)/(Wr·d1).

The layer parameters variation with time after HDG rebar (ZT) passivated with Permapass embedment in
concrete is shown in Figure 6a and 6b.
Immediately after rebar embedment in concrete, the corrosion products phase formed in the rebar vicinity was
much thicker compared to the concrete vicinity.
Twelve hours after rebar embedment in concrete, the corrosion products layer thickness in rebar vicinity reduces,
while the resistance relative to thickness increases compared to the concrete vicinity. This shows that a highly
resistant, dense corrosion products layer formed in rebar vicinity, and a less dense layer formed in the concrete
vicinity. It was assumed that the two concomitantly phenomena occurred: corrosion products formation in rebar vicinity
and their migration into the concrete matrix. These two phenomena develop with different rates. Thus, the layer in the
rebar vicinity densifies.
Twenty-four hours after rebar embedment in concrete, the corrosion products layer thickness and the resistance
relative to thickness increase in rebar vicinity, compared to the concrete vicinity. This shows the presence and
development of the corrosion products layer in rebar vicinity.
The measurements performed 36 and 48 hours after rebar embedment in concrete show an ongoing growth of
corrosion products phase in rebar vicinity. Its resistance relative to thickness continues to be 3-5 times higher
compared to that of the corrosion products phase in concrete vicinity. This shows that corrosion products phase in
concrete vicinity densifies. Such behavior shows and confirms the difference in rate of the two already mentioned
phenomena: the corrosion products formation and their migration into the concrete matrix.

(a) (b)
Fig. 6 - Evolution with time of the HDG rebar passivated with Permapass for: (a) corrosion products thickness in rebar vicinity and in concrete
vicinity ratio (n1); (b) (Rp·d2)/(Wr·d1) ratio / Evoluția în timp în cazul armăturii zincate termic pasivate cu Permapass a: (a) raportului dintre grosimea
fazei de oxid adiacente armăturii și grosimea fazei de oxid adiacente betonului (n1); (b) raportului (Rp·d2)/(Wr·d1).

The variation parameters with time after rebar embedment in concrete of HDG rebar (ZT) passivated with yellow
[Cr VI] is shown in Figure 7a and 7b.
Immediately after rebar embedment in concrete, the corrosion products layer thickness in rebar vicinity was
significantly lower while its resistance relative to thickness was much higher compared to the concrete vicinity. This
shows the presence of a thin, dense corrosion products phase in rebar vicinity, while the corrosion products phase in
concrete vicinity has a low density.
Twelve and 24 hours after rebar embedment in concrete, the two phases layers were approximately equal in
thickness while the resistance relative to thickness ratio was still significantly higher in the vicinity of concrete, showing
a dense corrosion products area in rebar vicinity and densifying in concrete vicinity. This behavior indicates the
ongoing formation of corrosion products on rebar surface with the formation rate higher than the migration rate into the
concrete matrix.
Thirty-six hours after rebar embedment in concrete, corrosion products layer thickness increases significantly in
rebar vicinity, and resistance suddenly drops, indicating the dense film dissolution and the formation of a more
permissive layer with a lower resistance. The resistance decrease was observed 48 hours after rebar embedment in
concrete. Thus, the corrosion products formation rate was very high, but the corrosion products continued to migrate
into the concrete matrix.

(a) (b)
Fig. 7 - Evolution with time of the HDG rebar passivated with yellow [CrVI] for: (a) corrosion products thickness in rebar vicinity and in concrete
vicinity ratio (n1); (b) Rp·d2)/(Wr·d1) ratio / Evoluția în timp în cazul armăturii zincate termic pasivate cu [CrVI] galben a: (a) raportului dintre grosimea
fazei de oxid adiacente armăturii și grosimea fazei de oxid adiacente betonului (n1); (b) raportului (Rp·d2)/(Wr·d1).

4. Conclusions

The experimental results obtained by electrochemical impedance spectroscopy (EIS) lead to the following
conclusions:
- Interpretation of experimental results in the form of Nyquist and Bode plots can be interpreted by fitting with an
equivalent electric circuit model;
- The best-fitted equivalent electrical circuit obtained shows that the corrosion products layer formed is
composed of two phases. One phase is in the rebar vicinity and the other phase is in the concrete vicinity. The two
phases density and resistance evolve independently, showing independent increase in thickness or density. Thus, the
hypothesis that the corrosion products layer that forms at the rebar/ concrete interface evolves uniformly and
constantly with time is infirmed.
Mathematical interpretation of the fitted equivalent electrical circuit parameters, using the n1 and n2 variation
parameters, lead to the following conclusions:
- In the case of the non-passivated HDG rebar, a corrosion products permissive layer forms on the metal
surface, immediately after rebar embedment in concrete. Twelve and 24 hours after rebar embedment in fresh
concrete, the corrosion products layer densifies in rebar vicinity, while the corrosion products layer remains permissive
to ions in concrete vicinity. Thirty-six hours after rebar embedment in concrete there is a significant increase in
corrosion products layer thickness in rebar vicinity. The corrosion products layer becomes permissive during growing
phase and 48 hours after rebar embedment in concrete the corrosion products layer thickness increases and densifies
in rebar vicinity.
- In case of HDG rebar passivated with Permapass, a corrosion products thick layer of low density forms in
rebar vicinity immediately after rebar embedment in concrete. During the first 12 hours, they most probably migrate
into concrete matrix. Thus, the layer thickness in rebar vicinity reduces, but it also densifies, while the layer thickness
in concrete vicinity increases. The corrosion products formation continues, and thus the layer thickness increases in
rebar vicinity.
- In the case of the HDG rebar passivated with yellow [Cr VI], corrosion products form immediately after rebar
embedment in concrete and migrate into concrete matrix, forming a thin and very dense layer in rebar vicinity, while
the layer formed in concrete vicinity is thicker and less dense. Between 12 to 24 hours after the rebar embedment in
concrete, the two corrosion products layers thicknesses are approximately equal. However, the layer in the rebar
vicinity is much denser. Subsequently it was found that the layer thickness increased in the rebar vicinity, while its
density decreased. This is a sign of layer dissolving and corrosion products strong migration into concrete matrix.
According to literature, HDG rebar surface activates in the highly alkaline environment of fresh concrete. Two
phenomena occur simultaneously during concrete solidification: the corrosion products formation and their migration
into concrete matrix. The fact that these two phenomena are simultaneous is particularly important, because unlike the
iron corrosion products (in the case of not-galvanized rebars), the corrosion products of HDG rebar migrate into the
concrete matrix. Thus is reduced the risk of internal stress accumulation at the interface, that could cause concrete
cracking and delamination. These two phenomena occur at different rates, depending whether passivation is used or
not, depending on the type of passivation used and on the concrete age (the contact duration with concrete).
Therefore, the two corrosion products layers thickness and density vary continuously.
A possible research direction would be to find the time duration of rebar contact with concrete until the
stabilization of corrosion products formation and migration rates. An ongoing stabilization sign might be the general
continuity of thickness and density variation of corrosion products layer. It is assumed that this stabilization can be
achieved around the concrete age of 28 days, when most of the concrete hydration-hydrolysis processes would be
completed and the concrete pH would be stabilized.
The novelty and scientific importance of this research is given by the use of EIS analysis method. This method
gives the opportunity to better understand the rebar/ concrete interface processes, and to characterize the corrosion
products layer evolution with time. Such understanding could not be obtained by conventional, destructive methods of
reinforced concrete analysis and, even less, by in-situ methods.

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