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Surface & Coatings Technology 306 (2016) 428438

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Surface & Coatings Technology

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Atmospheric corrosion evaluation of electrogalvanized, hot-dip


galvanized and galvannealed interstitial free steels using accelerated
eld and cyclic tests
Evandro de Azevedo Alvarenga, Vanessa de Freitas Cunha Lins
Chemical Engineering Department, Universidade Federal de Minas Gerais, Antonio Carlos Avenue 6627, 31270901, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Three years of outdoor corrosion tests, accelerated with a saline solution spray, and SAE J2334 and GM 9540P
Received 28 November 2015 accelerated corrosion tests of industrially coated electrogalvanized (GE), hot-dip galvanized (GI), galvanneal
Revised 24 March 2016 (GA) interstitial free steels were performed. The samples were industrially phosphatized and painted with a
Accepted in revised form 8 April 2016
modied epoxy resin, polyester resin as a primer and a base coat, and a high solid acrylic resin varnish as a
Available online 12 April 2016
clear coat. The effect of the deposition process and zinc mass on atmospheric corrosion of galvanized interstitial
Keywords:
free low-alloyed carbon steels was analyzed. The SAE J2334 test was more effective than the GM 9540P test in
Galvannealed differentiating the lowest corrosion resistance of the hot dip galvanized steel among the galvanized steels studied.
Electrogalvanized The duration of the accelerated eld test played an important role in the steel performance rating. The parameter
Hot dip galvanized of maximum corrosion penetration was more efcient to distinguish the effect of the zinc mass on corrosion
Accelerated eld test resistance of the galvanized steel samples evaluated using accelerated eld tests.
Atmospheric corrosion 2016 Elsevier B.V. All rights reserved.
Delamination

1. Introduction temperature [12]. Organic resins such as topcoat based on acrylic resins/
polyester/melamine and varnishes formulated with acrylic resin/
The search for galvanized and painted steels with optimized melamine were developed [13,14]. The incorporation of chromating
corrosion resistance for use in construction, automotive and home reagents in an acrylic lacquer applied on galvanneal and galvanized
appliance industries has motivated numerous research works [19]. steel was studied by Feliu and Barranco [15].
The electrogalvanized and galvanneal steels are the two most commonly Zinc alloy coatings have played an important role in improving the
used materials [10,11]. The latter is gaining more markets due to its low corrosion resistance of steels used in automotive, construction and
cost and excellent weldability conditions [9]. home appliance industries for the last thirty years [1,5]. Zinc coatings
The automotive paint system has brought innumerable im- act as an adherent barrier layer and as a cathodic protection [4]. Zn
provements, that apart from the multitude of available colors, based coatings may be obtained by electrodeposition, thermal spraying
higher brightness and paint elasticity, vibrant colors restricted to or immersion in liquid metal baths (hot-dipping) at 450 C [16,17]. The
certain sporting niches invade the popular car segment, such as most common industrial hot-dip (HD) zinc coatings used in Brazil are
green and blue that refers to ecology and sustainability. The auto- the GI (Zn0.2 wt.% Al), galvalume or Al55Zn (55 wt.% Al, 43.5 wt.%
motive paint system has also reached a better tribological and Zn, 1.5 wt.% Si), and galvanneal or GA which is obtained by annealing
chemical resistance [6]. To achieve this performance, the automo- at temperatures from 490 C to 540 C [4].
tive industry has invested in new types of pre-treatment such as The Zn layer of electrogalvanized and hot-dip (HD) galvanized steels
-mercaptopropyltrimethoxysilane (MTMO) [9]. New inorganic consists of the zeta phase. The galvanneal coating is composed of fragile
organic hybrid precursors for corrosion protective coatings on galvanized Fe\\Zn intermetallic compounds (IMCs), namely zeta-phase (monoclinic
iron were studied, and three different types of precursor sols, such as pure FeZn13: 5.86.5 wt.% Fe), palisade delta (FeZn10: 7.08.3 wt.% Fe), compact
boehmite, hydrolyzed 3-glycidyloxypropyltrimethoxysilane (GPS), and delta-phase (hexagonal FeZn7: 10.311.7 wt.% Fe), gamma-1 (face-
boehmiteGPS hybrid sols were prepared and deposited on ultrasonically centered cubic Fe5Zn21: 16.318.5 wt.% Fe), and gamma (body-centered
cleaned galvanized iron plates by using a dip coating technique at room Fe3Zn10: 22.228.2 wt.% Fe) [18]. The galvanneal coating contains approx-
imately 10 wt.% Fe, and its coating thickness is less than that of the HD
Corresponding author.
galvanized coatings [19]. The alloy coating on galvanneal is typically
E-mail addresses: evazal@hotmail.com (E. de Azevedo Alvarenga), vlins@deq.ufmg.br about 7 m in thickness [20]. Phase identication of IMCs in galvanneal
(V. de Freitas Cunha Lins). is crucial and was performed using techniques such as Mossbauer and

http://dx.doi.org/10.1016/j.surfcoat.2016.04.021
0257-8972/ 2016 Elsevier B.V. All rights reserved.
E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438 429

Table 1
Procedure of the SAE J2334 cyclic test.

Stage Test conditions Exposure (days of a week)

1 2 3 4 5 6 7

1ststage Relative moisture: N95% 6h 6h 6h 6h 6h


Humid chamber Temperature: 50 C 2 C
2nd Stage Saline solution: 0.5% m/v de NaCl + 0.1% 15 min 15 min 15 min 15 min 15 min
Salt spray wt./v de CaCl2 + 0.075% wt./v de NaHCO3,
Room temperature
3rd Stage Relative humidity: 50% 5% 17 h and 45 min 17 h and 45 min 17 h and 45 min 17 h and 45 min 17 h and 45 min
Dry chamber Temperature: 60 C 2 C
4th Stage Relative humidity: b50% 5% 24 h 24 h
Dry chamber Temperature: 60 C 2 C

The wet surface period of this test is 18% and the corrosion rate expected is 3.0 kg Fe/m2 year

Raman spectroscopy [20,21], transmission electron microscopy (TEM) 2. Material and methods
[22], Glow Discharge Optical Emission Spectroscopy (GDOES) [20], and
X-ray diffraction (XRD) [23]. IMCs volume fraction distribution denes The cold rolled steels used were interstitial free (IF) ultra-low carbon
the coating formability [18] and its main failure mode is the powdering, steel, electrogalvanized (GE) steels, and hot dip galvanized with heat
where particles with a mean size smaller than the coating thickness are treatment of the zinc layer (GA) and without heat treatment (GI). The
produced and powdered [17]. Powdering may be mitigated by controlling substrate of the coated steels was the IF ultra-low carbon steel with a
the Fe enrichment kinetics during the coating production [18]. nominal thickness of 0.8 mm. The steel samples were obtained from
Surface chemistry and morphology, alloy composition, phase industrial coils. The values of mass per area of metallic coatings for the
composition and the deposition process of zinc-iron coatings strongly GE steel were 45, 55 and 60 g/m2, for the GI steel were 40, 60 and
inuence their corrosion resistance [1,2426]. Specically, in the 80 g/m2 and for the GA steel were 40 g/m2 and 60 g/m2. The values of
automotive industry, hot-dip Zn-based coatings are often applied thickness of the zinc layer were 5.6, 6.3, 7.7, and 8.4 m for 40, 45, 55,
to interstitial free (IF) steels due to the ductility necessary for deep and 60 g/m2 of zinc mass per area, respectively.
drawing [27]. The samples for the corrosion tests with dimensions of 100 mm
Recently, Santos et al. [4] performed a comparative study of the 150 mm were processed in a Brazilian automotive industry. The phos-
electrochemical behavior of industrially coated hot-dip galvanized and phate used was tricationic and the painting consisted of the following
galvanneal steels. However, the atmospheric corrosion behavior of steps: electrophoretic painting process with a modied epoxy resin
these steels including the electrogalvanized steel, evaluated using the (thickness of 19 1.2 m), polyester resin as a primer (thickness of
accelerated eld test, is scarce in literature. Yadav et al. [28] have inves- 35.0 2.8 m) and a base coat (thickness of 18.0 0.9 m), and a high
tigated the effect of Fe\\Zn alloy layers which are formed during the solid acrylic resin varnish as a top coat (thickness of 40.0 3.1 m).
hot-dip galvanizing process on the corrosion resistance of galvanized The values of thickness of painting layers are shown in Table 3.
steel under atmospheric marine environment by using an accelerated The edges of each specimen as well as the areas containing identi-
wetdry cyclic corrosion test, potentiodynamic polarization, surface cation marks were protected by a coating of two-component epoxy
potential measurement, and AC impedance techniques. Silva et al. [29] polyamide. The paint lm on one side of each sample was mechanically
have also described the corrosion resistance of galvannealed steel scratched by a machining tool with a tungsten carbide tip, which
under marine atmosphere. Yadav et al. [28] have discussed the role reached the base metal, forming an internal angle of 60 15. The
such layers play in enhancing the protective ability of zinc corrosion scratch was made on the sample diagonally. The distance between the
products considering atmospheric corrosion. A comparative study end of the scratch and the edge was 20 mm, according to the NBR
of atmospheric corrosion resistance of industrially painted electro- 8754 Brazilian standard.
galvanized, hot-dip galvanized and galvannealed steels using the accel- The thickness of the dry paint lm was measured according to the
erate eld test with spray of a saline solution and cyclic tests is not NBR 10443 standard, and the adhesion was evaluated by using the
found in literature. The effect of the deposition process and the mass draw method. The adhesion of the dried paint lm was measured
of zinc coating on the atmospheric corrosion resistance of galvanized afxing pullout pins of 12.7 mm in diameter on the paint surface. The
steels is discussed. adhesive used was the two-component type: Huntsman Aradur 1012
The accelerated eld test is advantageous mainly for joining a (aliphatic polyamine) hardener and a DER 383 liquid epoxy resin
reduced test time, a low cost, and the simulation of the condition in provided by Dow Plastics (Dow Chemical Company), at a ratio of 35/
service, exposing the steels to an industrial atmosphere with a saline 65 parts of hardener by parts of resin. The pins were detached by
spray.

Table 2
Procedure of the GM 9540P accelerated cyclic corrosion test.

Stage Conditions

1st Stage Application of salt spray for 15 min 0.9% wt./v of NaCl + 0.1% wt./v of CaCl2 plus 0.25% wt./v of NaHCO3, pH = 6.0 a 8.0 Repeated 4 times before the next step
Intervall of 75 min Wet chamber at 25 C 2 C without salt spray
2nd Stage 2 h in wet chamber 25 C 2 C and relative humidity N30%
3rd Etapa 8 h in wet chamber 49 C 2 C and relative humidity between 95% and 100%
4th Etapa 7 h in dry chamber 60 C 2 C and relative humidity b30%
5th Stage 1 h in dry chamber 25 C 2 C and relative humidity b30%

Wet surface of the test period is 48% and the corrosion rate expected is 12.0 kg/m2 year
430 E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438

energy dispersive spectrometer (EDS), and to the 500i INCA wavelength


dispersion spectrometer (WDS), Oxford Equipment.

2.1. SAE J2334 cyclic test

The duration of the SAE J2334 test was 4320 h, and the testing
procedure is shown in Table 1. The equipment used was the Q-Fog
Q-Panel Company with a volume of 1100 L. The time period of the wet
surface of this test was 18% and its corrosiveness as measured by ve
uncoated carbon steel samples was 3.0 kg Fe/m2 per year.

2.2. GM 9540P cyclic test

The duration of the GM9540P test was 1920 h, corresponding to


80 cycles of 24 h. The samples were subjected to 160 cycles. The proce-
dure is shown in Table 2. The equipment used was the Q-Fog Q-Panel
Company with a volume of 1100 L. The time period of wet surface
(8) of the test was 37% and its corrosiveness as measured by ve
uncoated carbon steel samples was 12 kg Fe/m2 year.

2.3. Field test with a saline spray

The eld test with intermittent spraying of a saline solution was


performed exposing the specimens under standard atmospheric corro-
sion stations. The saline solution was sprayed twice a week. The NaCl
solution of 3% by weight, according to the ISO 11474:2014 standard
was sprayed using 100 mL volumetric asks until wetting the
metal surfaces. The corrosion station is located at an altitude of
247 m and 19o 2909 S latitude and 42 o 3201 W longitude. All
samples were analyzed simultaneously being subject to the same
climatic conditions.
The wet surface of this test period was 50% and the corrosiveness
was of 2.6 kg Fe/m2 year, well above that of the marine environment
which was 0.6 kg Fe/m2 year. The classication of the testing atmosphere
was C5 according to the ISO 9223 standard, a very high aggressiveness.
The eld test with saline spray required shorter exposure time than
the non-accelerated eld test and provided a lower cost of implementa-
tion in relation to the cyclic accelerated corrosion tests performed in the
laboratory. Depending on the number of weekly sprays applied to the
specimens, the test time can be reduced without compromising the
corrosion mechanism [30].
After completion of the corrosion tests, the advancement of corro-
sion from the scratch (the scribe delamination) and the maximum
corrosion penetration were evaluated for each sample. The average
advancement of corrosion is the amount of paint detachment from the
surface of the metal substrate along the mechanical damage, and the
corrosion is related to the cosmetic product. The maximum penetration
of corrosion is also measured along the scratch but in the direction of the
thickness, i.e., perpendicular to the body surface of the test piece and is
related to the structural strength of the steel. For each sample, ve
replicates were analyzed and the average value of scribe delamination
and the maximum value of corrosion penetration were considered.

3. Results and discussion

3.1. Morphology of coated samples


Fig. 1. SEM images of electrogalvanized, GE (a), hot dip galvanized, GI (b) and
galvannealed, GA (c) steels with a zinc layer of 60 g/m2.
The morphologies of metal coatings are shown in Fig. 1. According to
Fig. 1a, the GE steel zinc layer is formed by relatively small zinc crystals,
hexagonal and randomly oriented. The X-ray diffraction analysis per-
formed on the zinc layer only identied the eta phase (hexagonal zinc),
mechanical tensile test, using a PATTI adhesion test model 110 Elcometer and a preferred crystallographic texture of zinc crystals of low angle
pneumatic gauge. pyramidal planes. This characteristic is peculiar to the process used in
The morphology of the zinc or zinc alloy layer was evaluated using the production of GE steel [30,31].
scanning electron microscopy (SEM), an EVO 50 ZEISS scanning electron The zinc crystals of the GI steel layer are of the type minimized
microscope, with a voltage acceleration of 20 kV coupled to the 350 INCA (Fig. 1b). X-ray diffraction results identied the eta-phase as the single
E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438 431

Fig. 2. Average scribe delamination of steels with a zinc layer of 60 g/m2 submitted to: (a) the SAE J2334 cyclic test for 4320 h, (b) the GM 9540P cyclic test for 3840 h.

Fig. 3. Surfaces of ultra-low carbon, C\


\Mn (a), electrogalvanized, GE (b), hot dip galvanized, GI (c) and galvannealed, GA (d) steels submitted to 4320 h of the SAE J2334 cyclic test.
Galvanized steels with a zinc mass of 60 g/m2.
432 E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438

Fig. 4. Surfaces of ultra-low carbon, C\


\Mn (a), electrogalvanized, GE (b), hot dip galvanized, GI (c) and galvannealed, GA (d) steels submitted to 3840 h of the GM 9540P cyclic test.
Galvanized steels with a zinc mass of 60 g/m2.

phase present in the zinc layer of GI steel and the crystals showed a Figs. 3 and 4 show the samples after the SAE J2334 and GM 9540P
unique crystallographic texture of basal planes (Fig. 1b). These charac- cyclic tests. The SAE testing was more effective in differentiating the
teristics resulted from a hot galvanizing process used in the production lowest corrosion resistance of the hot dip galvanized steel among the
of the GI steel [30,31]. galvanized steels studied. The SAE J2334 test is less aggressive to the
The metallic coating of GA steel showed a rough surface (Fig. 1c). steel than the GM 9540P test in which the rst stage of application of
According to the XRD results, the metallic coating consists of the inter- 15 min of saline spray was repeated four times before the next step.
mediate IMCs: (FeZn13), (FeZn7), and (Fe3Zn10). The presence of
typical rod crystals of the zeta phase () and columnar crystals of the 3.3. Accelerated eld test
delta phase () were conrmed by SEM analysis (Fig. 1c). The roughness
of the GA steel metallic coating, due to the aforementioned phases, According to the data shown in Table 3 and Figs. 5 and 6, the steel
created an efcient anchoring surface for paint schemes [31]. coated with zinc and its alloys showed a higher corrosion resistance
than the IF ultra-low carbon steel (no metal coating), therefore showing
3.2. Accelerated cyclic tests the importance of the metal coating for the quality and service life of the
products manufactured with steel. The atmospheric corrosion mecha-
Analyzing the SAE J2334 and GM 9540P test results, the corrosion nism of iron is reported in literature [3234]. The primary reaction
performance of different types of galvanized, phosphatized and painted products formed on iron steel are hydrated Fe2+ ions which are further
steels was clearly discernible. oxidized by oxygen to Fe3+ and then precipitated as oxides, hydroxides
The galvannealed steel (GA) showed the highest corrosion resistance and oxyhydroxides (FeOOH). The thus formed rust layer has a large in-
among the coated steels, and the hot dip galvanized steel (GI) showed the uence on the further development of the corrosion process [34].
lowest (Fig. 2a and b). The painting layer showed the lowest adherence on the surface of
As for GE and GI steels, the average advancement of corrosion the IF carbon steel which was totally oxidized after three years of
observed in Fig. 2 (SAE J2334 GE = 2.7 0.8 mm, GI = 4.0 1.1 mm; exposure to an industrial atmosphere with a saline spray applied
GM 9540P GE = 5.5 1.1 mm, GI = 6.2 0.8 mm) are attributed to twice a week. Water can penetrate the painting coating through pores
the morphology of the metallic coating. in the organic lm causing swelling and reaching the paint-metal inter-
The higher corrosion resistance of GE steels than the GI steels, face. After disbounding of the painting lm, the non-uniform dissolution
evaluated using accelerated cyclic tests, is attributed to morphology of of carbon steel resulted in coarse unevenness at the rust-steel interface,
the zinc layer of the GE steel (Fig. 1a) which is rougher and more effective and a non-uniform formation of -FeOOH and an amorphous ferric
in anchoring the paint lm than the zinc layer of the GI steel. oxyhydroxide [32,34]. The rust layer showed many cracks giving rise to

Table 3
Results of the eld test with an intermittent saline spray.

Steel Painting layer Oxidized area (%)


3 years
Thickness Adherence
(m) (MPa)

Ultra low carbon steel 121 7.5 0.55 0.05 100 0


97% A/C
GE 60/60 g/m2 124 7.2 2.02 0.23 22.0 1.6
0% A/C
GI 60/60 g/m2 116 14.4 0.63 0.06 21.0 1.5
86% A/C
2
GA 40/40 g/m 122 12.2 2.29 0.05 35.0 2.0
0% A/C
2
GA 60/60 g/m 133 5.5 2.10 0.10 3.0 0.1
0% A/C
E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438 433

Fig. 5. Average scribe delamination (a) and maximum corrosion penetration (b) of IF ultra-low carbon, electrogalvanized (60 g/m2), hot-dip galvanized (60 g/m2) and galvannealed (40
and 60 g/m2) steels after 3 years of a eld test with saline spray.

paths for water, oxygen, and other corrosives which contribute to the exposure, the corrosion resistance of the 40/40 g/m2 galvannealed
total oxidation of the mild steel after three years [33,34]. steel (GA) was higher than that of the electrogalvanized (GE) and hot
Furthermore, the duration of the accelerated eld test played an dip galvanized steels (GI). In the third year of exposure there was an
important role in the steel performance rating. In the rst two years of abrupt increase in the average scribe delamination and in the
434 E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438

Fig. 6. Samples after three years of exposure in a eld test with saline spray: a) IF ultralow carbon steel, b) 60/60 g/m2 GE, c) 60/60 g/m2 GI, d) 40/40 g/m2 GA e) 60/60 g/m2 GA.

maximum penetration of corrosion of the GA steel with a metallic When zinc is oxidized, zinc hydroxide is produced in accordance with
layer of 40/40 g/m2 and its corrosion resistance became inferior to Eq. (1) or the compound ZnCl2.4 Zn (OH)2 is formed in environments
that of GE and GI steel, reaching the total thickness loss as shown containing chloride ions (Cl) [36,37].
in Fig. 5b.
The metallic coating mass inuenced the corrosion resistance of the Zn 2H2 OZnOH2 2H 2e 1
steel [31], as shown in Table 3 and Fig. 5: the greater the mass of metal
coating the smaller the average scribe delamination and the smaller the The presence of this compound inhibits the oxygen reduction reaction,
maximum corrosion penetration. Eq. (2) [36].
The type of metal coating affected the corrosion resistance of the
steel as shown in Table 3 and Fig. 5. Among the electrogalvanized O2 2H2 O 4e 4OH 2
(GE), hot dip galvanized (GI), and galvannealed (GA) with zinc mass
of 60 g/m2, the GA steel showed the lowest scribe delamination. This Zhang [38] reports the presence of O/Zn ratios consistent with ZnO
result can be explained by the morphology of the metal coating of the in the outer 15 nm of the surface layer on zinc with ZnCO3 or Zn(OH)2
GA steel, which presented intermediate intermetallic phases of Fe\\Zn deeper into the lm. The extreme outer layer (1 nm) is rich in surface
and had a roughness that helped in xing the paint scheme, improving contaminants such as chlorine and sulfur [38]. LeBozek et al. [39]
paint adherence. Table 3 shows that the GA steels showed higher values reported the zinc hydroxyl carbonate and zinc hydroxyl chloride as
of painting adherence independent of the zinc mass per area. The zinc corrosion products of galvanized steels submitted to accelerated
morphology of the metal coating of the 40/40 g/m2 GA steel also cyclic corrosion tests. In this work, EDS analysis of corrosion region
explains the fact that its performance was better than that of GE and of galvanized steels indicated the presence of zinc, oxygen, chloride
GI steel in the rst two years of exposure. The smoother surface of the and carbon compatible to the existence of zinc hydroxyl carbonate
GI steel (Fig. 1b) produced the lowest adherence of the painting lm and zinc hydroxyl chloride [39]. These compounds, such as zinc carbonate
among the galvanized steels. This result contributed to a higher value and zinc hydroxide, act as barriers to the passage of ions and electrons,
of maximum corrosion penetration of GI steel than the GE and GA steels inhibiting the cathodic half- reaction, and hence the growth of the oxides.
with 60 g/m2 of zinc mass (Fig. 5b). The oxygen reduction reaction was also inhibited in the samples studied
However, as the zinc mass was smaller for the 40/40 g/m 2 GA containing phosphate and electrocoat layers deposited prior to paint
than for the 60/60 g/m2 GA, its barrier and cathodic protection was application and the delamination process is slower than in directly
also lower, and as zinc was consumed by the corrosion process, it painted metals.
left the steel exposed to environmental conditions, allowing the Literature reports that corrosion products produced on hot-dip
acceleration of the corrosion process in the third year of exposure galvanized steels showed a higher electric conductivity and were a
(Figs. 5 and 6). less efcient barrier than the corrosion products formed on Zn-Al-Mg
The corrosion process was greatly inuenced by the nature, stability coatings, for example [40].
and morphology of the corrosion product [35], which during the eld Among GE, GI and GA steels, it was observed that the corrosion
tests was formed, detaching the paint lm from the metal substrate, mechanism is dependent on the mass of metal coating. When zinc is
thus generating the wedge effect as shown in Fig. 7. The corrosion consumed, there remains the corrosive process of the uncoated steel
front is highlighted in Fig. 7a, d, f, g and h. whose corrosion product is bulkier and appears above the paint lm.
The corrosion process was more pronounced in the C\\Mn steels, The 40/40 g/m2 GA steel (Fig. 7f), which had smaller zinc mass, suffered
because their oxides are bulkier (thickness N 3.0 m) and less adherent more corrosion on the metal substrate; the thickness of its oxide in the
compared to the GE, GI, GA 40/40 g/m2 and GA 60/60 g/m2 steels, whose mechanical damage region (2.5 m) was close to the carbon steel
oxide thicknesses were 0.2 m, 0.7 m, 2.5 m and 0.3 m, respectively. (3.0 m), shown in Fig. 7a. EDS analysis of the damage region of carbon
These iron oxides produced a most signicant wedge effect contributing steel identied iron and oxygen as the main elements and traces of
to the detachment of the paint lm. chlorine.

Fig. 7. SEM micrograph of transversal section of IF ultra-low carbon steel (a), EDS spectrum of oxide on IF steel surface, area 1 of Fig. 7a, (b), SEM micrograph of transversal section of GE
steel (c), EDS spectrum of oxide on GE (area 1) and GI (area 1) surface (d), SEM micrograph of transversal section of GI steel (e), SEM micrograph of transversal section of 40/40 g/m2 GA
steel (f), SEM micrograph of transversal section of 60/60 g/m2 GA steel (g), and EDS spectrum of oxide on 60 g/m2 GA interface, area 2 of Fig. 7 g (h), after eld tests with saline solution
spray.
E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438 435
436 E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438

Table 4
Mass of zinc layer, thickness and adherence of the dry paint layer of steels studied.

Steel Mass of metallic coating(g/m2) Dry paint coating

Thickness Adherence
(m)

IF ultra-low carbon ULC Not applicable 112.2 7.7 Grade 0


Electrogalvanized GE45 44.3 1.8 107.2 7.8 Grade 0
GE55 54.7 2.0 110.6 8.0 Grade 0
Hot-dip galvanized GI40 40.9 0.2 107.6 7.7 Grade 0
GI60 60.8 1.2 110.8 7.2 Grade 0
GI80 81.5 1.1 115.8 8.1 Grade 0
Galvannealed GA40 39.7 0.9 107.4 7.4 Grade 0
GA60 62.0 1.7 107.6 7.2 Grade 0

a) grade 0 no detachment of the paint layer, grade 465% of detachment of the paint layer

Fig. 8. Average scribe delamination of IF ultra-low carbon steel, eletrogalvanized steels (45 and 55 g/m2), hot-dip galvanized steels (40, 60 and 80 g/m2) and galvannealed steels (40 and
60 g/m2) after three years of exposure in a eld test with spray of saline solution according to the ISO 11474 standard.

Corrosion was initiated at the mechanical defect in the coating with electrogalvanized steels, 40, 60 and 80 g/m2 for the hot dip galvanized
the exposure of zinc to environment as shown in Fig. 7c, e, f and g [32]. steels, and of 40 and 60 g/m2 for the galvannealed steels.
EDS analysis of the damage region identied iron and oxygen as main These steels were exposed to an industrial atmosphere for three
elements, the presence of zinc and chlorine in lesser concentration as years with a saline solution spray. Analyzing the results shown in
shown in Fig. 7d, indicating an advanced stage of the corrosion process. Figs. 8 and 9, the parameter of maximum corrosion penetration was
The cations produced undergo hydrolysis, acidifying the corrosion more efcient to distinguish the effect of the zinc mass on corrosion
region. Chloride ions then migrate into the local acidic environment. resistance of the galvanized steel samples. The 40 g/m2 and 60 g/m2
The corrosion process progresses under the paint lm as the corrosion GA steels showed the same scribe delamination, but maximum penetra-
products were being formed and the paint suffered delamination [38, tion of 0.17 and 0.07 mm after three years of exposure in accelerated
4143]. The organic coating suffered disbonding from the steel caused eld test.
by the wedging effect of the corrosion products [32]. EDS analysis of The highest atmospheric corrosion resistance of the galvannealed
region 2 of the transversal section of 60 g/m2 GA steel (Fig. 7g), localized steel is evident in Fig. 10. The best performance of the galvannealed
at the interface of corroded and intact area (corrosion front), showed steel can be attributed to the characteristics of its metallic coating. The
the presence of zinc, chlorine and oxygen as main elements, and traces heat treatment applied to the metallic coating of galvannealed steel dur-
of iron and carbon as shown in Fig. 7h. ing its production process provided the formation of intermetallic solid
solutions of iron and zinc, represented by columnar rod crystals of the
phase (FeZn13) and faceted granules of (FeZn7) phase, which assist in
3.4. Effect of zinc mass on atmospheric corrosion resistance anchoring paintings schemes. Furthermore, the presence of iron in its
metallic coating causes the electrochemical potential to become nobler
Table 4 shows the mass of zinc layer, thickness, and adherence of the and also permits the formation of a certain amount of phosphophilite dur-
dry paint layer of steels with a zinc mass of 45 and 55 g/m2 for the ing the phosphating process. The phosphophilite improves the phosphate
E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438 437

Fig. 9. Maximum corrosion penetration in IF ultra-low carbon steel, eletrogalvanized steels (45 and 55 g/m2), hot-dip galvanized steels (40, 60 and 80 g/m2) and galvannealed steels (40
and 60 g/m2) after two years of exposure in a eld test with spray of saline solution according to the ISO 11474 standard.

Fig. 10. Samples after three years of exposure in a eld test with spray of saline solution according to the ISO 11474 standard.
438 E. de Azevedo Alvarenga, V. de Freitas Cunha Lins / Surface & Coatings Technology 306 (2016) 428438

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