coatings
Article
Structure and Corrosion Resistance of Coatings Obtained by the
Batch Double Hot Dip Method in Eutectoid ZnAl Bath with the
Addition of Mg and Si
Henryk Kania
Citation: Kania, H. Structure and
Corrosion Resistance of Coatings
Obtained by the Batch Double Hot
Dip Method in Eutectoid ZnAl Bath
with the Addition of Mg and Si.
Coatings 2022, 12, 1207. https://
doi.org/10.3390/coatings12081207
Academic Editor: Shijie Wang
Received: 26 July 2022
Accepted: 12 August 2022
Published: 18 August 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the author.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Coatings 2022, 12, 1207. https://doi.org/10.3390/coatings12081207
Department of Metallurgy and Recycling, Faculty of Engineering Materials, Silesian University of Technology,
Krasińskiego 8, 40-019 Katowice, Poland; henryk.kania@polsl.pl
Abstract: The article presents the results of the research determining the synergistic effect of Mg
and Si additives in the ZnAl23 bath on the microstructure (SEM), growth kinetics, and corrosion
resistance of coatings obtained by the batch double hot dip method. On the basis of the research on
the chemical composition in micro-regions (EDS) and the research on the phase composition (XRD),
the structural components of the coatings with a content of 3 and 6 wt.% Mg and 0.2–0.4 wt.% Si
were identified. The corrosion resistance of the coatings was compared with that of the reference
coating obtained in the ZnAl23Si0.4 bath in the neutral salt spray test (EN ISO 9227), and the test with
sulfur dioxide in a humid atmosphere (EN ISO 6988). The parameters of electrochemical corrosion
of the coatings were determined. This allowed for the conclusion that the addition of Mg and Si to
the ZnAl23 bath improved the microstructural uniformity of the coating. In the area of the diffusion
layer, the presence of the FeAl3 intermetallic phase was found, while in the outer layer the dendrite
of the Al-rich solution with interdendritic spaces, where it locates areas of Zn-rich solution, eutectic
Zn/MgZn2 or phase separation MgZn2 and Mg2 Si are located. Additions of Mg and Si stabilize the
kinetics of the coating’s growth, and its course is parabolic. The conducted corrosion tests showed
better corrosion resistance of the coatings obtained in the bath with Mg addition compared to the
reference coating obtained in the ZnAl23Si bath. The increase in corrosion resistance results from
the presence of a more anodic MgZn2 phase, which, however, may be weakened by the presence of
Mg2 Si phase precipitates.
Keywords: hot dip galvanizing; ZnAlMgSi coatings; corrosion resistance
1. Introduction
For many years, hot dip galvanizing coatings have been a commonly used anti-
corrosion protection applied in different industries. Zinc coatings have many advantages,
including providing a barrier and sacrificial corrosion protection for steel, and are resistant
to mechanical damage. Their use is constantly growing, covering an increasingly complex
range of products, including cast iron [1], heat-treated steel [2], or high-speed drawing
wires [3]. However, the growing requirements for corrosion resistance make products
protected with a zinc coating less and less attractive to the recipient. Moreover, the rising
prices of zinc caused by the growing demand for this metal, as well as its decreasing
reserves, make it necessary to look for ways to reduce its consumption. Therefore, the
market need necessitates the development of new, innovative coatings with increased
corrosion resistance, produced by a rational and economical method, which is the hot
dip process.
The addition of Al to the galvanizing bath significantly increases the corrosion re-
sistance of the coatings. Already in the 1970s and 1980s, the production of Galvalume
(AnAl55Si1.6) [4] Galfan (ZnAl5 + mishmetal) [5] coatings began. It is estimated that
their corrosion resistance is 2–4 times higher compared to traditional zinc coatings. An
https://www.mdpi.com/journal/coatings
Coatings 2022, 12, 1207 2 of 22

additional increase in the corrosion resistance of ZnAl coatings is caused by the addition
of Mg to the bath. The following coatings have been produced on an industrial scale for
several years: Suprer Zinc (Zn-4.5Al-0.1Mg) [6], Super Dyma (Zn-11Al-3Mg-0.2Si) [7],
ZAM (Zn-6Al-3Mg) [8] and MagiZincTM (Zn, 1–2 wt.% Mg, 1–2% Al) [9]. Coatings ob-
tained in baths containing large Al additives as well as Mg additives are currently produced
only by the continuous method on metal sheets. In this method, patented by T. Sendzimir,
prior to immersion in the bath, the steel strip is annealed at a temperature between 780 and
840 ◦ C in a reducing atmosphere containing N2 /H2 . Such conditions favor the reduction of
oxides on the surface of the steel, which guarantees continuous coverage; and the short
immersion time in the bath (a few s) does not cause excessive growth of the coating. Despite
many advantages, ZnAlMg coatings are not produced on an industrial scale by the unit
method, mainly due to the necessity to use fluxes, long immersion times, and the intensive
course of the reaction between the iron and the Zn-Al bath. The research carried out so far
allows us to state that the only reproducible method of producing Zn-Al-Mg coatings is the
use of a two-stage dip method, in which the ZnAlMg coating is produced on a previously
formed zinc coating [10].
In the two-component Zn-Al equilibrium system (Zn-Al binary system) eutectoid
transformation takes place at the content of 23 wt.% Al. Such an alloy is characterized
by the presence of a eutectoid structure which is a fine crystalline two-phase mixture.
Obtaining a coating with this structure is advantageous from the point of view of imparting
better ductility to the coating. Previous studies have shown that in the production of
coatings by the two-stage method in two-component ZnAl baths the content of eutectoid
and hypereutectoid Al leads to the formation of excessively thick coatings and porosity
susceptible to delamination. The growth of the coating under such conditions also causes
the formation of a periodical layered structure (PLS), characterizing the alternating structure
of the intermetallic phases layers of the FeAl system and the alloy layers of the metalizing
bath. A slight decrease in the reactivity of steel is caused by the addition of Mg to the
bath [11]. On the other hand, the coatings obtained in ZnAl baths containing Mg show
very good corrosion resistance [6–9]. An effective limitation of the reactivity of steel in
the ZnAl bath is the addition of Si. Mendala [12] showed that the addition of 1.6 wt.% Si
to the ZnAl55 bath reduces the excessive growth of the coating obtained by the batch
hot dip method even with a several-minute immersion time. The addition of Si stabilizes
the structure of the coating, which shows a layered structure of the Fe2 Al5 and FeAl3
intermetallic phases, which are covered by the outer layer of the alloy of the metalizing
bath. The addition of Si also has a positive effect on the thickness and structure of the
coatings obtained by the batch double dip method. Presence of 1–2 wt.% Si in the eutectoid
composition bath (ZnAl23) allows for the reduction of the excessive thickness of the coating
and obtains a favorable structure of the coating [13]. At the same time, Si does not cause an
excessive reduction of the coating thickness on high-silicon steels [14].
The paper discusses the synergistic effect of 3–6 wt.% Mg and 0.2–0.4 wt.% Si for
ZnAl23 bath on the cross-section microstructure and corrosion resistance of coatings ob-
tained by the batch double hot dip method. It seems that the synergistic interaction of Mg
and Si in the ZnAl23 bath will provide a favorable structure and thickness of the coating as
well as high corrosion resistance. The aim of the research is to produce new ZnAl23MgSi
coatings with increased corrosion resistance by batch hot-dip method, which will allow to
reduce the thickness of the coating and reduce material costs.

2. Materials and Methods

2.1. Preparation of Coating
Test coatings were prepared by double batch hot dip methods. First, the samples were
immersed in the conventional Zn bath at 450 ◦ C for 30 s. Immediately after being taken out
of the Zn bath, the samples were immersed in the ZnAl23MgSi bath for 30, 60, 120, and
240 s. The Al content in the bath was maintained at the eutectoid level −23 wt.%, while
the content of Mg was 3 and 6 wt.%, and the Si content −0.2 and 0.4 wt.%. The bath was
Coatings 2022, 12, 1207 3 of 22

prepared from the following batch materials: Super High-Grade Zinc, ZnAl4, and AlMg25
mortar. The chemical composition of the bath was determined using the ARL 3460 emission
spectrometer (Thermo ARL, Waltham, MA, USA) and is presented in Table 1.
Table 1. Chemical composition of research baths.

Content [wt.%]
Bath
Al Fe Si Mg Bi Sn Zn and Others
Zn 0.0068 0.032 0.001 0.002 0.0001 0.0003 residue
ZnAl23Mg3Si0.2 23.29 0.026 0.219 2.91 0.0014 0.0028 residue
ZnAl23Mg3Si0.4 22.84 0.022 0.391 2.83 0.0017 0.0031 residue
ZnAl23Mg6Si0.2 22.91 0.011 0193 5.89 0.0022 0.0035 residue
ZnAl23Mg6Si0.4 23.07 0.028 0.412 6.11 0.0031 0.0036 residue

After removal from the ZnAl23MgSi bath, the samples were cooled in air. The
ZnAlMgSi bath temperature was determined by the Al content. For technological rea-
sons, it was assumed that it would be at least 20 ◦ C higher than the solidification point of
the ZnAl23 alloy. Based on previous studies of the solidification point of ZnAl alloys [15],
the temperature of 510 ◦ C was assumed for all tested ZnAl23MgSi baths. The coatings
were made on samples with dimensions of 50 mm × 100 mm × 2 mm, made of S235JRG2
steel. The chemical composition of the steel was determined using the Spectro Lab M8
emission spectrometer (SPECTRO Analytical Instruments, Kleve, Germany) and presented
in Table 2.

Table 2. Chemical composition of S235JRG2 steel.

Content [wt.%]
Grade
C Si Mn S P Fe and Others
G235JRG2 0.138 0.021 0.743 0.0086 0.0088 residue

Before being immersed in the Zn bath, the samples were subjected to acid degreasing
by immersion in a HydronetBase solution for 5 min, pickling in 12% HCl solution for
10 min, rinsing in water, and fluxing in Tego-Flux60 solution for 2 min and drying at 120 ◦ C
for 15 min.

2.2. Microstructure Characterization

Initial assessment of the coating structure and thickness measurement on the cross-
section of the coating layers were performed using the Olympus-GX51 optical microscope
(OM) (Olympus Corporation, Tokyo, Japan). The analysis software Olysia m3 (Olympus
Corporation, Tokyo, Japan) was used to record the image and measure the thickness of
the coatings. On the corrosion test specimens, the thickness of the coatings was measured
by a non-destructive method using an electromagnetic meter Elcometer 355 (Elcometer,
Manchester, UK). The final result was the mean of the 10 measurements.
The study of the microstructure of the coatings at high magnifications and the study
of the chemical composition in the micro-regions were performed with a Hitachi S-3400 N
scanning electron microscopy (SEM) equipped with an energy dispersion spectroscope
(EDS) (Hi-tachi, Tokyo, Japan). Noran Instruments—System Six (Thermo Fisher Scientific,
Waltham, MA, USA) software was used for microstructure image (SEM) recording and
micro-area chemical composition (EDS) studies.
X-ray phase analysis was performed on a Philips X’Pert 3 X-ray diffractometer (Malvern
Panalytical, Malvern, UK) using a copper anode lamp (λCuKα = 1.54178 Å) ´ with a current
of 30 mA at 40 kV and a graphite monochromator. The recording was made continuously
with a step of 0.026◦ in the range from 10 to 90◦ 2θ. The tests were carried out on the
surface of the oblique grinding of the coating, including the phase composition over the
entire cross-section of the coating. ICDD PDF-2 and COD database were used to identify
the phase composition.
Coatings 2022, 12, 1207 4 of 22

2.3. Corrosion Resistance Characterization

The neutral salt spray test was performed in accordance with EN ISO 9227 [16]. A COR-
ROTHERM Model 610 salt chamber with a volume of 400 dm3 (Erichsen, Hemer, Germany)
was used for the tests. The tests were carried out in a mist of 5% NaCl solution in distilled
water at pH 6.8–7.2. The condensation rate of the mist on a plane surface of 80 cm2 was
1.5 ± 0.5 m/h. The temperature in the chamber was kept at 35 ± 1 ◦ C. The smoothness
and surface changes of the samples were monitored every 24 h. Gravimetric tests were
performed after 24, 48, 96, 240, 480, 720, 1000, and 1500 h of exposure in the chamber. No cor-
rosion products were removed from the surface of the samples before mass measurement.
The final result was the average of 5 samples of the same type and three measurements for
each sample.
Sulfur dioxide test in a humid atmosphere was performed according to EN ISO 6988 [17].
Koesternich Hygrotherm model 519 chambers with a working volume of 300 dm3 (Erichsen,
Hemer, Germany) were used for the tests. The daily cycle included 8 h exposition of samples
in a closed chamber and 16 h exposure in the ambient atmosphere. For each research cycle,
2 dm3 of distilled water was poured into the chamber and 0.2 dm3 of SO2 was added. The
exposure in a closed chamber was carried out at a temperature of 40 ± 1 ◦ C. The smoothness
and surface changes of the samples were monitored every 24 h. Gravimetric tests were
performed after each daily cycle. No corrosion products were removed from the sample
surfaces prior to mass measurement. The final result was the average of 5 samples of the
same type and three measurements for each sample. The total duration of the research was
30 daily cycles.
The recording of the potentiodynamic curves was carried out on a Potentiostat/Galvanostat
PG201 (Radiometer, Copenhagen, Denmark) using the Voltamaster 1 software (Radiometer,
Copenhagen, Denmark). Saturated calomel electrode (SCE) was used as a reference elec-
trode in the tests. A platinum electrode (Radiometer, Copenhagen, Denmark) was used as
an auxiliary electrode. In order to standardize the test results, the potential values were
converted to a normal hydrogen electrode (NHE) by shifting the measurement values by
244 mV. Potentiodynamic tests were carried out in a 3.5% NaCl solution in distilled water at
the temperature of 20 ◦ C. Before starting the tests, the surface of the samples was degreased
in trichlorethylene in an ultrasonic cleaner for 180 s, then rinsed with distilled water and
dried in a stream of air. The samples prepared in this way were placed in a holder providing
an active electrode surface of 1.0 cm2 . The measurement of the open cell potential lasted
about 5 min. After the open-circuit potential (OCP) was established, the dependence of
the current on the potential was recorded. These curves were the basis for determining the
potential (Ecorr ) and the corrosion current density (jcorr ). The electrochemical parameters of
the corrosion process were determined by extrapolation of Tafel curves.

3. Results and Discussion

3.1. Microstructure SEM, Chemical Composition EDS and Phase Composition XRD of Coatings
The microstructure of the coatings obtained in the ZnAl23 bath with Mg and Si
additions is shown in Figure 1 and Figures 3–5. Regardless of the alloying content in the
bath, the coatings have a layered structure, in which an outer layer and a diffusion layer can
be distinguished. However, these coatings, depending on the content of alloying elements,
show significant differences in the cross-section morphology.
The microstructure of the coating obtained in the Zn-23Al3Mg0.2Si bath is shown in
Figure 1. The percentages of the analyzed elements are given in Table 3. The presence of
Al-rich dendrites can be observed in the outer layer (Figure 1, point 1). The interdendritic
spaces are filled with a component rich mainly in Zn (Figure 1, point 4) and a component
rich in Zn and Mg (Figure 1, point 2). The XRD phase composition studies (Figure 2a)
confirm the presence of the Al and Zn on the cross-section of the coating. The structural
components of the coating in which Al (Figure 1, point 1) and Zn (Figure 1, point 4) are
found are therefore solid solutions of these metals. XRD tests confirmed the presence of
the MgZn2 intermetallic phase in the coating. It can therefore be argued, that these are
 confirm the presence of the Al and Zn on the cross-section of the coating. The st
components of the coating in which Al (Figure 1, point 1) and Zn (Figure 1, poi
found are therefore solid solutions of these metals. XRD tests confirmed the pre
the MgZn2 intermetallic phase in the coating. It can therefore be argued, that t
Coatings 2022, 12, 1207 5 of 22
interdendritic areas, in which high concentrations of Zn and Mg were found (F
point 2). This phase can also occur in the form of Zn/MgZn2 eutectic where in poi
a high content
interdendritic of in
areas, Znwhich
and Mg highis observed. There
concentrations of Zn are
and two zones
Mg were foundin the diffusion
(Figure 1, lay
coating.
point Atphase
2). This the substrate,
can also occurtheincompact
the form ofzone contains
Zn/MgZn 66.2 at.% Al and 22.1 at.% F
2 eutectic where in point 3 also
aas 5.2content
high at.% Zn and
of Zn 6.6Mg
and at.% Si (Figure
is observed. 1, point
There are two7,zones
Tablein 3).
theThe chemical
diffusion layer ofcomposi
the coating. At the substrate, the compact zone contains 66.2 at.% Al and
the Al:Fe atomic fraction close to 3:1 indicate that it is probably the intermetallic 22.1 at.% Fe as
well as 5.2 at.% Zn and 6.6 at.% Si (Figure 1, point 7, Table 3). The chemical composition
the FeAl3 system, which dissolves both Zn and Si. The presence of the FeAl3 inter
and the Al:Fe atomic fraction close to 3:1 indicate that it is probably the intermetallic
phaseofin
phase thethe
FeAlcoating was confirmed by the diffraction pattern in Figure 2a. In the
3 system, which dissolves both Zn and Si. The presence of the FeAl3
geneous zone
intermetallic phase ininpoint 5, a high
the coating concentration
was confirmed by theof Al and pattern
diffraction Fe is observed in a ratio
in Figure 2a.
In the(Table
3:1 heterogeneous
3). It alsozone in point the
suggests 5, a presence
high concentration of Al3 and
of the FeAl phaseFe isinobserved in a In po
this region.
ratio close to 3:1 (Table 3). It also suggests the presence of the FeAl3 phase in this region.
Fe concentration decreases, and the Zn content increases (Figure 1, Table 3). T
In point 6, the Fe concentration decreases, and the Zn content increases (Figure 1, Table 3).
measurement
The small measurementarea does not not
area does allow forfora areliable
allow determination
reliable determination of theof chemical
the chemical c
tion, but an
composition, butincrease in inZn
an increase Znconcentration
concentration may may indicate
indicate that
that the the heterogeneity
heterogeneity of the of t
structure
layer is filled
structure is filledwith
with aa zinc
zincsolution.
solution.

Figure
Figure 1. SEM
1. SEM microstructure
microstructure of the obtained
of the coating coatinginobtained in the ZnAl23Mg3Si0.2
the ZnAl23Mg3Si0.2 bath. bath.

Table 3. Chemical composition in micro-areas (EDS) of the coating obtained in the ZnAl23Mg3Si0.2
Table 3. Chemical composition in micro-areas (EDS) of the coating obtained in the ZnAl23
bath (analysis points as shown in Figure 1).
bath (analysis points as shown in Figure 1).
Content of Elements
Points of Content of Elements
Microanatysis
Points
Mg-K of Al-K Si-K Fe-K Zn-K
Mg-K Al-K Si-K Fe-K Z
wt.%Microanatysis
at.% wt.% at.% wt.% at.% wt.% at.% wt.% at.%
1 65.8
wt. %82.3
at. % - wt. % - at. % -wt. % -at. % 34.2 wt. % 17.7at. % wt.%
2 14.8 1
30.9 2.6 4.9 - 65.8 - 82.3 - - - - 82.6 - 64.2- 34.2
3 4.9 12.0 0.9 2.0 - - - - 94.2 86.0
4 -
2- 3.3
14.87.6 30.9 - 2.6 - 4.9 - - -
- 96.7
- 92.4
- 82.6
5 - 3- 42.1 4.9 59.8 12.0 4.4 0.9 6.0 2.0 28.2 - 19.4 - 25.3 - 14.8- 94.2
6 - - 36.9 56.5 2.1 3.1 17.8 13.2 43.2 27.3
7 -
4- 50.4
- 66.2 - 5.2 3.3 6.6 7.6 34.8 - 22.1 - 9.6
- 5.2
- 96.7
5 - - 42.1 59.8 4.4 6.0 28.2 19.4 25.3
6 - - 36.9 56.5 2.1 3.1 17.8 13.2 43.2
Coatings 2022, 12, x FOR PEER REVIEW 6 of 22

Coatings 2022, 12, 1207 6 of 22

7 - - 50.4 66.2 5.2 6.6 34.8 22.1 9.6 5.2

Figure 2.2.Diffractogram
Figure Diffractogram of theofoblique ground surface
the oblique ground of coatings
surfaceobtained in the bath:
of coatings (a) ZnAl23Mg3Si0.2;
obtained in the bath: (a)
(b) ZnAl23Mg3Si0.4; (c) ZnAl23Mg6Si0.2; (d) ZnAl23Mg6Si0.4.
ZnAl23Mg3Si0.2; (b) ZnAl23Mg3Si0.4; (c) ZnAl23Mg6Si0.2; (d) ZnAl23Mg6Si0.4.

Increasing the Si content to 0.4 wt.% in the ZnAl23Mg3 bath does not change the
Increasing the Si content to 0.4 wt.% in the ZnAl23Mg3 bath does not change the
phase composition of the coating. The presence of the same phases was identified in the
phase composition of the coating. The presence of the same phases was identified in the
diffraction pattern (Figure 2b) from the surface of the diagonal cut of the coating. However,
diffraction pattern (Figure 2b) from the surface of the diagonal cut of the coating. How-
the phase morphology on the cross-section of the coating clearly changes (Figure 3). There
ever, the phase
is no zone with amorphology
heterogeneous on the cross-section
structure of the coating
in the diffusion layer ofclearly changesDirectly
the coatings. (Figure 3).
There is no zone with a heterogeneous structure in the diffusion
on the substrate, a compact layer is formed with a content of 59.4 at.% Al and 20.6 at.% layer of the coatings.
Fe
Directly on the substrate, a compact layer is formed with a content
and 10.6 at.% Zn and 9.4 at.% Si (Figure 3, point 7, Table 4). The Al:Fe ratio is close of 59.4 at.% Al andto 20.6
at.% Feratio,
the 3:1 and 10.6
whichat.%mayZnindicate
and 9.4 at.% Si (Figure
the presence of 3,
thepoint
FeAl7, Table 4).
3 phase The Al:Fe
in which bothratio
Zn andis close
to the dissolved.
Si are 3:1 ratio, which maychemical
A similar indicatecomposition
the presencewas of thefoundFeAl phase
in3 the in whichinboth
precipitates Zn6 and
point
Si are dissolved.
(Figure 3, Table 4).AThese
similar chemicalhave
precipitates composition
a regular was shape found
and arein the precipitates
located in point 6
mainly directly
(Figure 3, Table 4). These precipitates have a regular shape and are located mainlylayer
on the dense diffusion layer, but single precipitations are also observed in the outer directly
of the
on the coating. The diffusion
dense diffusion layer, but layer obtained
single in the ZnAl23Mg3Si0.4
precipitations are also observed bathinhas
theaouter
muchlayer
smaller
of thicknessThe
the coating. which is caused
diffusion by the
layer influence
obtained in of
thea higher Si content inbath
ZnAl23Mg3Si0.4 the bath.
has aThe much
presence of the FeAl phase in the coating was clearly confirmed by
smaller thickness which is caused by the influence of a higher Si content in the bath. The
3 the diffraction pattern
shown in of
presence Figure 2b. 3The
the FeAl presence
phase in the of Al-rich
coating wasdendrites
clearly is visible inby
confirmed thethe
outer layer of pattern
diffraction the
coating (Figure 3, point 4). These dendrites are surrounded by a more heterogeneous layer
shown in Figure 2b. The presence of Al-rich dendrites is visible in the outer layer of the
(Figure 3, point 3). Both areas forming dendrites containing Al and Zn (Table 4, points 3
coating (Figure 3, point 4). These dendrites are surrounded by a more heterogeneous layer
and 4) slightly differ in the proportion of individual metals. The chemical composition
(Figure
and phase 3, composition
point 3). Both areas2b)
(Figure forming
indicatedendrites
the presence containing
of a solid Alsolution
and Znof(Table 4, points
Al in Zn and 3
and
Zn in4)Al.slightly differ in thespaces
The interdendritic proportion of individual
are filled metals. The
with areas containing Mg chemical composition
and Zn (Figure 3,
and phase composition (Figure 2b) indicate the presence of a
point 5), as well as the Zn/MgZn2 eutectic mixture (Figure 3, points 1 and 2). The chemicalsolid solution of Al in Zn
and Zn in Al.in
composition The interdendritic
micro-areas spaces
in points are 2filled
1 and and inwith areas
point containing
5, as well as the Mg and Zn
results of (Figure
the
3, point
phase 5), as well tests
composition as the Zn/MgZn
(Figure 2 eutectic
2b), confirm themixture
presence(Figure 3, points
of the solid 1 and 2).
Al solution Theand
in Zn chem-
ical composition
the MgZn 2 phase in micro-areas
these areas. in points 1 and 2 and in point 5, as well as the results of
the phase composition tests (Figure 2b), confirm the presence of the solid Al solution in
Zn and the MgZn2 phase in these areas.
Coatings 2022,12,
Coatings2022, 12,1207
x FOR PEER REVIEW 77 of
of 22
22

Figure3.3.SEM
Figure SEMmicrostructure
microstructureof
ofthe
thecoating
coatingobtained
obtainedin
inthe
theZnAl23Mg3Si0.4
ZnAl23Mg3Si0.4bath.
bath.

Table4. 4.
Table Chemical
Chemical composition
composition in the in the micro-areas
micro-areas (EDS)
(EDS) of the of obtained
coating the coating
in the obtained in the
ZnAl23Mg3Si0.4
ZnAl23Mg3Si0.4 bath (analysis points
bath (analysis points as shown in Figure 3).as shown in Figure 3).

Content of Elements
Points of Content of Elements
Points of Mg-K Al-K Si-K Fe-K Zn-K
Microanalysis
Mg-K Al-K Si-K Fe-K Zn-K
Microanalysis wt. % at. % wt. % at. % wt. % at. % wt. % at. % wt.% at. %
wt.% at.% wt.% at.% wt.% at.% wt.% at.% wt.% at.%
1 - - 1.2 2.9 - - - - 98.8 97.1
1 - 2 - 1.2
3.1 2.9
7.7 1.7 - 3.8 - - -- - - - 98.895.2 97.188.4
2 3.1 7.7 1.7 3.8 - - - - 95.2 88.4
3 - - 41.8 63.5 - - - - 58.2 36.5
3 - - 41.8 63.5 - - - - 58.2 36.5
4 4 62.6 80.2 62.6 - 80.2 - - -- - - - 37.437.4 19.819.8
5 12.7 527.5 12.7
2.1 27.5
3.8 2.1 - 3.8 - - -- - - - 85.285.2 68.568.5
6 - 6 - 40.3
- 56.8
- 6.7
40.3 56.8 9.16.7 33.5
9.1 22.8 19.5
33.5 22.8 19.5 11.3 11.3
7 -
7 - 43.2
- 59.4
- 43.27.1 59.4 9.47.1 31.0
9.4 20.6
31.0 20.618.718.7 10.6
10.6

Themicrostructure
The microstructureof ofthe
thecoating
coatingobtained
obtainedin inthe
theZnAl23
ZnAl23bath bathcontaining
containing66wt.% wt.%Mg Mg
and0.2
and 0.2wt.%wt.%Si Siisisshown
shownin inFigure
Figure4.4. With
Withhigher
higherMg Mgcontent
contentin inthe
thebath,
bath,the
theouter
outerlayer
layer
ofthe
of thecoating
coatingisisformed
formedby byAl-rich
Al-richdendrites
dendrites(Figure
(Figure4a, 4a,point
point2). 2). On
On thethe other
other hand,
hand, no no
characteristic areas
characteristic areas of ofthe
theZn/ZnMg
Zn/ZnMg22 eutectic
eutectic mixture
mixture are areobserved.
observed. The The interdendritic
interdendritic
spacesare
spaces aremainly
mainlyfilled
filledwith
witha aphase
phasecontaining
containing35.135.1at.%
at. %
Mg,Mg,58.458.4
at.%at.%
ZnZnandand6.56.5
at.%at.Al%
Al (Figure
(Figure 4a, point
4a, point 1). The
1). The results
results of the
of the XRD XRD
phasephase composition
composition studies
studies (Figure
(Figure 2c) indi-
2c) indicate
cate itthat
that it isMgZn
is the the MgZn 2 phase.
2 phase. TheThe diffusion
diffusion layer
layer shows
shows a zonal
a zonal structure.InInthe
structure. thezone
zoneof of
non-homogeneous
non-homogeneousstructure, structure,there areare
there areas with
areas a content
with a contentof 56.2 at.%at.%
of 56.2 Al, 18.2 at.% at.%
Al, 18.2 Fe and Fe
15.7
andat.%
15.7 Zn at.%(Figure 4c, point
Zn (Figure 4c, 3, Table
point 3,5). The 5).
Table heterogeneity of the structure
The heterogeneity of this layer
of the structure is
of this
filled
layer by the Zn-rich
is filled by the(Figure
Zn-rich4c, point 4c,
(Figure 4) and Al-rich
point 4) andareas (Figure
Al-rich areas4c, point 6).
(Figure 4c, In order
point 6). to
In
clearly
order to visualize the differences
clearly visualize in the structure
the differences in the of this zone,
structure Figure
of this zone,4d Figure
presents 4ditspresents
image
obtained
its imagewith the use
obtained of secondary
with the use ofelectrons
secondary (SE). The results
electrons (SE).ofThe
theresults
XRD phase of thecomposition
XRD phase
studies
composition (Figure 2c) indicate
studies (Figurethat the FeAlthat
2c) indicate 3 intermetallic phase and solid
the FeAl3 intermetallic phasesolutions
and solidof Al
solu-
in Zn and Zn in Al occur in the diffusion layer of heterogeneous
tions of Al in Zn and Zn in Al occur in the diffusion layer of heterogeneous structure. On structure. On the other
hand,
the othera compact
hand, alayer with layer
compact a composition of 65.5 at.%ofAl65.5
with a composition andat.%
21.4Al at.%andFe21.4
is formed
at.% Feonis
the substrate, also including Si and Zn (Figure 4c, point 7). A similar
formed on the substrate, also including Si and Zn (Figure 4c, point 7). A similar composi- composition can be
observed
tion can be in observed
the precipitates spreading inspreading
in the precipitates the zone of in the
the inhomogeneous diffusion layer
zone of the inhomogeneous dif-
(Figure
fusion layer4c, point
(Figure5). 4c,
When
pointanalyzing
5). When the chemical
analyzing thecomposition in micro-areas
chemical composition and the
in micro-areas
phase
and the composition obtainedobtained
phase composition on the cross-section of the coating,
on the cross-section of the itcoating,
shoulditbeshould
statedbe that the
stated
areas in points 5 and 7 correspond to the FeAl phase in which Si
that the areas in points 5 and 7 correspond to the FeAl3 phase in which Si and Zn dissolve.
3 and Zn dissolve.
Coatings 2022,12,
Coatings2022, 12,1207
x FOR PEER REVIEW 8 of 228 of 22

(a) (b)

(c) (d)
Figure
Figure4.4.SEM
SEM microstructure of the
microstructure of coating obtained
the coating in the bath
obtained ZnAl23Mg6Si0.2:
in the (a) coating(a) coating
bath ZnAl23Mg6Si0.2:
cross-section, (b) diffusion layer (c) micro-area A—backscattered electron (BSE) image,
cross-section, (b) diffusion layer (c) micro-area A—backscattered electron (BSE) image, (d)(d)
micro-
micro-area
area A—secondary electron (SE) image.
A—secondary electron (SE) image.
Table 5. Chemical composition in the micro-areas (EDS) of the coating obtained in the
Table 5. Chemical
ZnAl23Mg6Si0.2 composition
bath in the as
(analysis points micro-areas (EDS) of
shown in Figure 4).the coating obtained in the ZnAl23Mg6Si0.2
bath (analysis points as shown in Figure 4).
Content of Elements
Points of
Mg-K Al-K of Elements
Content Si-K Fe-K Zn-K
Points of Microanalysis.
Mg-K wt. % Al-K
at. % wt. % at. %Si-K wt. % at. % wt. %
Fe-K at. % wt.% at. %
Zn-K
Microanalysis
1 17.6 35.1 3.6 6.5 - - - - 78.8 58.4
wt.% at.% wt.% at.% wt.% at.% wt.% at.% wt.% at.%
2 0.5 0.7 68.3 83.6 - - - - 31.2 15.7
1 17.6 35.1 3.6 6.5 - - - - 78.8 58.4
3 - - 36.7 56.2 1.3 1.9 24.6 18.2 37.4 23.6
2 0.5 0.7 68.3 83.6 - - - - 31.2 15.7
3 - 4 - 0.2
36.7 0.5 56.2 6.3 1.3 13.9 1.9 24.6 5.2 18.25.5 88.3
37.4 80.123.6
4 0.2 5 0.5 -6.3 - 13.944.0 60.5 6.3 8.3 5.2 30.0 5.519.9 19.7
88.3 11.280.1
5 - 6 - 0.4
44.0 0.6 60.564.8 6.3 81.4 -8.3 - 30.0 - 19.9- 34.8
19.7 18.011.2
6 0.4 7 0.6 64.8 0.3 81.451.1 65.5
0.2 - 4.8- 6.1 - 33.4 21.4 - 34.8 6.6 18.0
12.2
7 0.2 0.3 51.1 65.5 4.8 6.1 33.4 21.4 12.2 6.6
The microstructure of the coating obtained in the ZnAl23Mg6 bath with increasing
the SiThe
content to 0.4 wt.% of
microstructure is the
shown in Figure
coating 5. The
obtained in cross-section
the ZnAl23Mg6 morphology
bath withitself does the
increasing
not differ significantly. In the diffusion layer, it can be observed the presence of dense
Si content to 0.4 wt.% is shown in Figure 5. The cross-section morphology itself does not
layer on the substrate (Figure 5, point 7), which then turns into a heterogeneous zone (Fig-
differ significantly. In the diffusion layer, it can be observed the presence of dense layer
ure 5, points 5 and 6). The analysis of the chemical composition in these EDS micro-areas
on the substrate (Figure 5, point 7), which then turns into a heterogeneous zone (Figure 5,
(Table 6) and the results of the XRD phase composition tests (Figure 2d) allow us to iden-
points 5 and 6). The analysis of the chemical composition in these EDS micro-areas (Table 6)
tify these structural components of the coating as the FeAl3 phase, which dissolves Zn and
and the results of the XRD phase composition tests (Figure 2d) allow us to identify these
Si. In the outer layer of the coating, dendrites with a significant content of Al and Zn are
structural components of the coating as the FeAl phase, which dissolves Zn and Si. In the
formed (Figure 5, point 4). Directly in their vicinity,3 areas with a similar chemical compo-
outer layer of the coating, dendrites with a significant content of Al and Zn are formed
sition containing small amounts of Mg can be observed (Figure 5, point 2). The interden-
(Figure
dritic 5, point
spaces 4). Directly
are mainly filled in their
with the vicinity,
phase inareas
whichwith a similar
the content of chemical
29.2 at.% composition
Mg and
containing small amounts of Mg can be observed (Figure 5, point
62.0 at.% Zn and 8.8 at.% Al (Figure 5, point 3, Table 6) was identified. 2).The
TheXRD
interdendritic
phase
spaces are mainly filled with the phase in which the content of 29.2 at.% Mg and 62.0 at.% Zn
and 8.8 at.% Al (Figure 5, point 3, Table 6) was identified. The XRD phase composition
studies (Figure 2d) allow the conclusion that these structural components of the coating
Coatings 2022, 12, x FOR PEER REVIEW 9 of 22

Coatings 2022, 12, 1207 9 of 22

composition studies (Figure 2d) allow the conclusion that these structural components of
the coating form Al and Zn solid solutions and the ZnMg2 phase. At the content of 6 wt.%
Mgform
andAl and Zn solid
increasing solutions
the Si contentand the bath
in the ZnMgto2 phase.
0.4 wt.%At it
the content
can of 6 wt.%
be observed Mg
the and
interaction
increasing the Si content in the bath to 0.4 wt.% it can be observed the interaction of these
of these elements with each other. This leads to the formation of a new structural compo-
elements with each other. This leads to the formation of a new structural component in
nent in the coating in the outer layer. The chemical composition determined in point 1
the coating in the outer layer. The chemical composition determined in point 1 (Figure 5,
(Figure
Table 5,
6) Table
and the6)XRD
andphase
the XRD phase composition
composition studies
studies (Figure (Figurethat
2d) indicate 2d)it indicate
is the Mgthat it is
2 Si
thephase.
Mg2SiThephase. The
Mg2 Si Mgwas
phase 2Si phase was not
not observed in observed inobtained
the coatings the coatings
in theobtained
baths withinlower
the baths
with lower Mg and
Mg and Si content. Si content.

Figure 5. SEM
Figure microstructure
5. SEM microstructure of the coating
of the coatingobtained
obtainedin in
thethe ZnAl23Mg6Si0.4
ZnAl23Mg6Si0.4 bath.bath.

Chemical composition
Table6.6. Chemical
Table in thein
composition micro-areas (EDS) of the(EDS)
the micro-areas coating of
obtained
the in the ZnAl23Mg6Si0.4
coating obtained in the
bath (analysis points
ZnAl23Mg6Si0.4 bathas(analysis
shown inpoints
Figure 5).
as shown in Figure 5).

Content of Contentof Elements

Elements
Points of Points of
Microanalysis
Mg-K Mg-K
Al-K Al-K Si-K Si-K Fe-K Fe-K Zn-K Zn-K
Microanalysis
wt.% at.% wt.%
wt.% at.% at.% wt.%wt.% at.%at.%wt.% wt.%
at. % wt.
at.% % at. wt.% % wt.%
at.% at. %
1 50.3 1 53.9 50.3
- 53.9- - 49.7 - 46.149.7 -46.1 -- - -- -
2 - 2 - 64.6
- 81.7
- -
64.6 81.7 - - - - - - 35.2
- 18.3
35.2 18.3
3 14.2 29.2 4.8 8.8 - - - - 81.1 62.0
4 0.8 3 1.0 14.2
67.8 29.2
83.1 4.8 - 8.8 - - - - -- -
31.4 81.1
15.9 62.0
5 0.6 4 1.6 0.8
21.8 1.0
39.9 67.8 83.1 - - - -
77.4 31.4
58.5 15.9
6 0.2 0.3 37.2 55.9 2.7 3.9 25.1 18.2 34.8 21.6
5 0.6 1.6 21.8 39.9 77.4 58.5
7 0.1 0.1 54.1 69.8 3.3 4.1 36.3 22.6 6.2 3.3
6 0.2 0.3 37.2 55.9 2.7 3.9 25.1 18.2 34.8 21.6
7 0.1 0.1 54.1 69.8 3.3 4.1
The formation of the coatings in the two-component ZnAl23 36.3 bath 22.6
leads to 6.2
the for-3.3
mation of a periodic layered structure, which causes the formation of porous coatings of
The formation
excessive thickness.of the
The coatings
addition in the
of Mg two-component
to the bath reduces thisZnAl23 bath but
phenomenon, leads to not
does the for-
mation of a periodic layered structure, which causes the formation of porous
eliminate it completely [11]. The research shows that the addition of Si to the bath helps to coatings of
excessive thickness.
inhibit the formationTheof aaddition of Mg structure.
periodic layered to the bath Thereduces
mechanism thisofphenomenon, but does
Si interaction raises
notmuch
eliminate it completely
controversy so far and [11]. Themainly
is known researchfromshows that theofaddition
the production coatings inofaluminum
Si to the bath
baths.
helps Si occupies
to inhibit theaformation
large number of of vacancieslayered
a periodic in the crystallographic
structure. The network of the Fe
mechanism of2 Al
Si5inter-
phase [18]. According to Riabov [19], it blocks the paths of easy diffusion
action raises much controversy so far and is known mainly from the production of of aluminum in coat-
this phase. According to another hypothesis, in the presence of Si, a triple
ings in aluminum baths. Si occupies a large number of vacancies in the crystallographic Fe-Al-Si phase
is formed, which seed and grows slower than the Fe2 Al5 phase [20]. Selverian et al. [21]
network of the Fe2Al5 phase [18]. According to Riabov [19], it blocks the paths of easy dif-
observed in the ZnAl55Si1.7 bath the formation of the Al-Fe-Zn-Si intermetallic compound
fusion of aluminum in this phase. According to another hypothesis, in the presence of Si,
on the substrate/coating interface, which transformed into the Fe2 Al5 phase after a longer
a triple
time. Fe-Al-Si
Similarly,phase
Hondaisetformed, which seed
al. [22] detected Zn and andSigrows slower thancompound
in an intermetallic the Fe2Alformed
5 phase [20].

Selverian et al. [21] observed in the ZnAl55Si1.7 bath the formation

on a steel substrate in a ZnAlMgSi bath. Moreover, they confirmed that the obtained of the Al-Fe-Zn-Si
intermetallic compound on the substrate/coating interface, which transformed into the
Fe2Al5 phase after a longer time. Similarly, Honda et al. [22] detected Zn and Si in an in-
termetallic compound formed on a steel substrate in a ZnAlMgSi bath. Moreover, they
Coatings 2022, 12, 1207 10 of 22

intermetallic compound has the same orthorhombic crystal structure as the Fe2 Al5 phase.
According to the authors [22], in the Al-Zn-Si system, Fe dissolution into the liquid phase
is significantly suppressed by the presence of a thin layer of Si-containing Fe2 Al5 phase at
the coating/substrate interface. They claim that it is very likely that the Fe2 Al5 phase with
dissolved Si and Zn is an Al-Fe-Si intermetallic compound.
The tests carried out in the ZnAl23 bath, regardless of the content of Mg and Si, did
not confirm the presence of the Fe2 Al5 phase. However, tests showed the presence of the
FeAl3 phase in the coating. The research on the structure of coatings obtained in baths
containing Al, Mg, and Si additives, which has been carried out so far, is not unequivocal.
Ranjan et al. [23] claim that in the ZnAl21 bath containing the Si addition, the Fe2 Al5 phase
containing dissolved Zn and Si is formed at the interface between the coating/substrate.
According to Perrot et al. [24] in the initial phase of the layer growth, the FeAl3 phase is
formed, which then goes into the Fe2 Al5 phase. According to Peng et al. [25], the reaction
of Fe with the Zn-Al bath leads to an increase in the intermetallic phases FeAl3 and Fe2 Al5
containing dissolved zinc. However, McDevitt [26] claims that in the baths with low Al
content, the FeAl3 phase is first formed, which then undergoes transformation, leading
to the formation of a Fe2 Al5 phase layer at the boundary with the substrate. Similarly,
Horstmann [27] believes that in the bath with a higher Al content, the FeAl3 phase layer
grows first until it reaches the thickness at which it transforms at the border with the
substrate into the Fe2 Al5 phase. The lack of the Fe2 Al5 phase in the tested coatings does
not allow us to unequivocally exclude its presence or its transformation. However, the
presence of two layers of FeAl3 and Fe2 Al5 phases in the coating is the reason for stresses,
which explains the formation of an unfavorable periodic layered structure. According to
Selverian et al. [21], the increase of the Fe2 Al5 phase layer causes a significant increase in
volume. This leads to stresses at the substrate/coating interface. The increase in stress
causes fracture and detachment of this phase layer as it grows. Severian et al. [21] also
show the presence of stresses at the Fe2 Al5 /FeAl3 interface, which leads to cracking and
delamination of the FeAl3 phase layer and the formation of a periodic layered structure.
The tested coatings, regardless of the chemical composition of the bath, did not detach from
the substrate or tend to form a periodic layered structure. Thus, it can be assumed that
even the hypothetical existence or transformation of the Fe2 Al5 phase in the coating, the
amount of which is beyond the detectability of the research methods used, will not affect
the properties of the coating.
The tests carried out have shown that Mg is present mainly in the outer layer of
the coating. With the content of 3 wt.% Mg in the bath are randomly distributed areas
of the MgZn2 phase or Zn/MgZn2 eutectic, which are located in interdendritic spaces.
Increasing the content of Mg to 6 wt.% causes the MgZn2 phase to completely fill the
interdendritic spaces. There are no Zn/MgZn2 eutectic regions in this case. Increasing the
Si content to 0.4 wt.% leads additionally to the formation of randomly distributed Mg2 Si
phase precipitates in the outer layer. Xie et al. [28] showed that the formation of the MgZn2
intermetallic phase in coatings obtained in eutectic ZnAl baths is possible at a content
above 3 wt.% Mg. Also, Liu et al. [29] claim that the MgZn2 phase is formed at higher
Mg contents in the bath. According to Gao et al. [30], Mg in coatings obtained in baths
with 15–55 Al wt.% and 0.5–3.0 Mg wt.% is in the elemental form and is not present in
the intermetallic Zn-Mg system in the coating. By contrast, Honda et al. [22] identified
the presence of both the MgZn2 phase and the Mg2 Si phase in coatings obtained in the
ZnAl11Mg3Si0.2 bath.

3.2. Kinetics of Growth

The relationship between the average thickness of the total coatings obtained in the
ZnAl23 bath with the addition of Mg and Si and the immersion time in the bath is shown
in Figure 6a. With all coatings, it can be seen that the overall thickness gain is slower with
increasing immersion time. Thickness changes of coatings obtained in baths containing
3 wt.% Mg, regardless of the Si content, are similar and after an immersion time of 240 s,
 Coatings 2022, 12, 1207 11 of 22

they reach the values of 45.12 ± 2.23 µm, respectively, with a value of 0.2 wt.% Si in the bath
and 37.09 ± 2.42 µm with 0.4 wt.% Si in the bath. A similar thickness of 41.78 ± 2.09 µm
Coatings 2022, 12, x FOR PEER REVIEW has a coating obtained in a bath containing 6 wt.% Mg and 0.2 wt.% Si. On the other 12 ofhand,
22
the coating obtained in the ZnAl23Mg6Si0.4 bath has a much greater thickness. After an
immersion time of 240 s, it was 74.13 ± 2.58 µm.

100 14
Zn-23Al3Mg0.2Si Zn-23Al3Mg0.2Si
Zn-23Al3Mg0.4Si
total thickness of of coatings [mm]

12 Zn-23Al3Mg0.4Si
Zn-23Al6Mg0.2Si y = 0.53x0.54
80 Zn-23Al6Mg0.2Si
R2 = 0.98
Zn-23Al6Mg0.4Si
10 Zn-23Al6Mg0.4Si

thickness [mm]
y = 0.45x0.53
60 R2 = 0.99
8

6
40 y = 0.38x0.41
R2 = 0.98
4
20 y = 0.17x0.52
2 R2 = 0.99

0 0
0 50 100 150 200 250 0 50 100 150 200 250 300
time [s] time [s]

(a) (b)
20
y = 8.59x0.14
R²= 0.99
18
y = 9.25x0.11
R²= 0.98
thickness [mm]

16 y = 8.38x0.13
R²= 0.99

14

Zn-23Al3Mg0.2Si
12
Zn-23Al6Mg0.2Si
Zn-23Al6Mg0.4Si
10
0 50 100 150 200 250 300
time [s]

(c)
Figure Figure
6. Growth kinetics
6. Growth of research
kinetics coatings:
of research (a) total
coatings: thickness
(a) total of the
thickness of coating, (b) (b)
the coating, thickness of the
thickness of the
compact layer and (c) thickness of the layer with a heterogeneous structure.
compact layer and (c) thickness of the layer with a heterogeneous structure.

3.3. Corrosion
TheResistance
coating formed in the hot dip process is formed in two steps. During immersion
3.3.1. Material andthe
in the bath, diffusionResearch
Reference layer grows, and after the product is removed from the bath, it
becomes covered with a layer of liquid melt. The diffusion layer grows as a result of simul-
The corrosion resistance of the coatings obtained in the ZnAl23 bath with the addi-
taneous partial processes of diffusion growth, dissolution, and secondary crystallization,
tion ofwhich
Mg and Si was its
determine compared in the[31].
final thickness same corrosion
These test with
regularities theaffect
do not reference coating of
the formation
obtained
thein the coating
outer ZnAl23Si0.4
layer, bath without
and its the depends
thickness additionmainly
of Mg.on The
theZnAl23Si0.4
viscosity of coating
the liquid
was prepared by the double hot dip method on a sample of the same
alloy from which the coated product is drawn. Under these conditions, steel grade and with
a mathematical
the same immersion
description parameters
of the as werekinetics
coating growth used for the changes
from production of coatings
in the in baths
overall coating with
thickness
the addition of Mg.impossible.
is practically The chemical Thecomposition of the
growth kinetics ZnAl23Si0.4
of the bath is presented
Fe-Al intermetallic in Ta-the
layer forming
ble 7. diffusion layer can be described by the equation [32]:
n
y = k × bath.
Table 7. Chemical composition of reference ZnAl23Si0.4 t (1)

Content [wt.%]
Bath
Al Fe Si Mg Bi Sn Zn and Others
ZnAl23Si0.4 23.14 0.021 0.397 0.0003 0.0017 0.0026 residue
Coatings 2022, 12, 1207 12 of 22

where:
y—thickness of intermetallic layer [µm].
k—growth rate constant [µm/sn ].
t—growth time [s].
n—growth-rate index.
In the kinetics equations of compact layer growth shown in Figure 6b, it can be
observed that in the case of three baths the index “n” of the growth-rate is 0.53 respectively
for the coating obtained in the ZnAl23Mg3Si0.2 bath; 0.52 for the coating obtained in the
ZnAl23Mg6Si0.2 bath and 0.54 for the coating obtained in the ZnAl23Mg6Si0.4 bath. The
“n” growth-rate index value close to 0.5 indicates that the growth of the compact layer is
parabolic and thus diffusion-controlled [32]. A slightly lower value of the growth-rate index
“n” 0.41 was observed for the coating obtained in the ZnAl23Mg3Si0.4 bath. Thus, the
growth of the compact layer is slower here. In the structure of this coating in the transition
layer, there was no zone with a heterogeneous structure (Figure 3). Direct contact of the
compact layer with the liquid alloy intensifies the dissolution processes, which reduces
the rate of layer growth. The values of the significantly lowest growth-rate index “n”
were obtained for the heterogeneous zone. Its value is 0.14; 0.11 and 0.13 respectively
for ZnAl23Mg3Si0.2, ZnAl23Mg6Si0.2 and ZnAl23Mg6Si0.4 baths (Figure 6c). This layer
grows much slower due to increased dissolution due to direct contact with the liquid
ZnAlMgSi alloy.

3.3. Corrosion Resistance

3.3.1. Material and Reference Research
The corrosion resistance of the coatings obtained in the ZnAl23 bath with the addition
of Mg and Si was compared in the same corrosion test with the reference coating obtained
in the ZnAl23Si0.4 bath without the addition of Mg. The ZnAl23Si0.4 coating was prepared
by the double hot dip method on a sample of the same steel grade and with the same
immersion parameters as were used for the production of coatings in baths with the
addition of Mg. The chemical composition of the ZnAl23Si0.4 bath is presented in Table 7.
Table 7. Chemical composition of reference ZnAl23Si0.4 bath.

Content [wt.%]
Bath
Al Fe Si Mg Bi Sn Zn and Others
ZnAl23Si0.4 23.14 0.021 0.397 0.0003 0.0017 0.0026 residue

Before starting the corrosion tests, the structure was revealed and the coating thickness
was determined on a reference sample. The reference coating obtained in the ZnAl23Si0.4
bath (Figure 7) shows a two-layer structure. Its structure is similar to the structure of the
coating produced in the ZnAl bath with a eutectoid composition containing the addition of
1 wt.% Si [13]. In the outer layer of the coating, the presence of areas of solid solutions of Al
in Zn (α) and Zn in Al (β) can be observed. The diffusion layer is composed of the FeAl3
intermetallic phase, the zone of which near the substrate has a compact structure, which in
the outer zone turns into a heterogeneous structure. In the coating, one can also observe
the occurrence of Si precipitates at the boundary between the transition layer and the outer
layer of the coating.
The average thickness of the ZnAl23Si0.4 coating on the reference sample is 40.43 ± 1.32 µm.
The thickness of this coating is in the comparable thickness range of the tested coatings
obtained in ZnAl23MgSi baths. The list of coating thicknesses on samples for corrosion
tests is presented in Table 8.
 containing the addition of 1 wt.% Si [13]. In the outer layer of the coating, the pre
areas of solid solutions of Al in Zn (α) and Zn in Al (β) can be observed. The d
layer is composed of the FeAl3 intermetallic phase, the zone of which near the s
has a compact structure, which in the outer zone turns into a heterogeneous stru
Coatings 2022, 12, 1207 13 of
the coating, one can also observe the occurrence of Si precipitates at the 22
boundary
the transition layer and the outer layer of the coating.

Figure
Figure 7. Structure
7. Structure of theof the reference
reference coating in
coating obtained obtained in the bath
the ZnAl23Si0.4 ZnAl23Si0.4 bath
for corrosion for
tests. corrosion
Table 8. The average thickness of coatings on samples for corrosion tests.
The average thickness of the ZnAl23Si0.4 coating on the reference sample i
The Thickness of Coatings (µm)
1.32 µ m. The thickness of this coating is in the comparable thickness range of th
ZnAl23Si0.4 ZnAl23Mg3Si0.2
coatings obtained in ZnAl23MgSi ZnAl23Mg3Si0.4
baths. TheZnAl23Mg6Si0.2
list of coatingZnAl23Mg6Si0.4
thicknesses on sam
40.43 ± 1.32 34.54 ± 1.87 31.42
corrosion tests is presented in Table 8. ± 1.82 33.81 ± 1.72 42.08 ± 2.24

3.3.2. The Neutral Salt Spray Test

Table 8. The average thickness of coatings on samples for corrosion tests.
The corrosion resistance of the coatings in the neutral salt spray was assessed on the
basis of unitary mass changes during Thethe Thickness
test in relationoftoCoatings
the reference coating obtained in
(µm)
the ZnAl23Si0.4 bath. The change in the unitary weight of the ZnAl23MgSi coating during
ZnAl23Si0.4 ZnAl23Mg3Si0.2 ZnAl23Mg3Si0.4 ZnAl23Mg6Si0.2 ZnAl23M
exposure to neutral salt spray is shown in Figure 8. During the corrosion test, all tested
40.43showed
coatings ± 1.32 mass gains.
34.54 At± 1.87
the same time, 31.42 ± 1.82 obtained33.81
all coatings in the ± 1.72
Mg-containing 42.08 ±
baths showed a smaller unitary weight gain compared to the reference coating obtained in
the ZnAl23Si0.4
3.3.2. The Neutralbath without the addition
Salt Spray Test of Mg. The lowest weight gain during exposure
to the salt spray chamber was shown by the coatings obtained in the bath containing
3 wt.%TheMg. corrosion
After 1500 hresistance of the coatings
of test the unitary weight gain in of
thetheneutral
coating salt
was spray was assesse
respectively
2 for the coating obtained in the ZnAl23Mg3Si0.2 bath and 8.89 g/m2 for the
basis of unitary mass changes during the test in relation to the reference coating
8.65 g/m
coating
in the obtained
ZnAl23Si0.4 in the ZnAl23Mg3Si0.4
bath. The change bath.inThe
theunitary
unitary mass changeofcurves
weight of coatings
the ZnAl23MgSi coa
obtained in baths containing 3 wt.% Mg during the test shows a similar course regardless
ing exposure to neutral salt spray is shown in Figure 8. During the corrosion test, a
of the Si content in the bath. Coatings obtained in baths containing 6 wt.% Mg show larger
coatings
unitary showed
weight gains. mass gains. At the
After completion same
of the time,test,
corrosion all the
coatings
unitaryobtained
weight gain inwas
the Mg-co
baths
9.67 g/mshowed
2 a smaller
for the coating unitary
obtained in theweight gain compared
bath containing 0.2 wt.% Si toandthe reference
10.92 g/m for coating
2 a
coating obtained in a bath containing 0.4 wt.% Si. With a value of
in the ZnAl23Si0.4 bath without the addition of Mg. The lowest weight gain duri6 wt.% Mg, greater weight
gain
surewasto observed for the chamber
the salt spray coating obtained in the bath
was shown by with a higher Siobtained
the coatings concentration.
in theAtbath co
the same time, in the corrosion test, the reference coating obtained in the ZnAl23Si0.4 bath
3 wt.%theMg.
showed After
highest 1500gain.
weight h ofAttest the ofunitary
the end weight
the corrosion test,gain
it wasof13.60
the g/m
coating
2. was resp
8.65Theg/m 2 for the coating obtained in the ZnAl23Mg3Si0.2 bath and 8.89 g/m2 for
corrosion resistance tests of alternative coatings obtained in the ZnAl23Mg bath
ing obtained
without in the
the addition ZnAl23Mg3Si0.4
of Si, conducted so far, bath.showed The unitary weight
comparable mass change
gains in curves
the of
neutral salt spray test (NSS test) (according to EN ISO 9227). The
obtained in baths containing 3 wt.% Mg during the test shows a similar course re unitary weight gain of
the coating obtained in the ZnAl23Mg3 bath was 8.126 g/m2 , while the coating obtained in
of the Si content in the bath. Coatings obtained in baths containing 6 wt.% Mg sho
the ZnAl23Mg6 bath was 9.31 g/m2 [33]. On the basis of the unitary mass increase of the
unitaryproducts,
corrosion weight itgains.
can beAfter completion
concluded that the Siof the corrosion
content test, not
in the bath does thesignificantly
unitary weight g
9.67 the
affect g/m 2 for theresistance
corrosion coating of obtained in the
the coatings. bath containing
However, the presence0.2 wt.%
of Si in theSibath
andis10.92 g
coating obtained in a bath containing 0.4 wt.% Si. With a value of 6 wt.% Mg
weight gain was observed for the coating obtained in the bath with a h
 Coatings 2022, 12, 1207 14 of 22

Coatings 2022, 12, x FOR PEER REVIEW

advantageous as it stabilizes the structure of the coating and reduces its thickness. The14 of 22
thickness of the coatings obtained in the ZnAl23Mg baths without the addition of Si was
much greater and ranged from 110–120 µm [33]. At the same time, both in the case of the
tested ZnAl23MgSi coatings and ZnAl23Mg coatings [33] can be noticed that the addition
concentration. At the same time, in the corrosion test, the reference coating obtained in
of 3 wt.% Mg to the bath significantly reduces the growth of corrosion products. On the
the ZnAl23Si0.4 bath showed the highest weight gain. At the end of the corrosion test, it
other hand, higher Mg contents in the bath (6 wt.%) contribute to an increase in the amount
was
of 13.60 g/m
corrosion
2.
products on the surface of the coating, thus lowering its corrosion resistance.

Figure8.8.Dependence
Figure Dependenceofof unitary
unitary changes
changes in the
in the massmass of coatings
of coatings obtained
obtained in the in the research
research baths baths
duringthe
during theneutral
neutral salt
salt spray
spray test.
test.

Figure 9 showsresistance
The corrosion the surface appearance
tests of ZnAl23Si0.4,
of alternative ZnAl23AlMg3Si0.4,
coatings obtained in the ZnAl23Mg and bath
ZnAl23AlMg6Si0.4 coatings after 1500 h exposure in the salt chamber.
without the addition of Si, conducted so far, showed comparable weight gains in the neu- After comple-
tion
tral of thespray
salt corrosion test, the
test (NSS coatings
test) did nottopenetrate
(according EN ISOthe substrate,
9227). which confirms
The unitary weight theirgain of the
very high corrosion resistance. The coating obtained in the2ZnAl23Si0.4 bath (Figure 9a)
coating obtained in the ZnAl23Mg3 bath was 8.126 g/m , while the coating obtained in the
shows the highest proportion of white corrosion products on the surface. White corrosion
ZnAl23Mg6 bath was 9.31 g/m2 [33]. On the basis of the unitary mass increase of the cor-
products are identified as zinc or aluminum corrosion products [34]. It is also evident that
rosionwhite
more products, it can
corrosion be concluded
products remain on that
thethe Si content
surface of the in the bath
coating does in
obtained notthesignificantly
bath
affect the corrosion resistance of the coatings. However, the
containing 6 wt.% Mg (Figure 9c) than on the surface of the coating obtained in the presence of Si in bath
the bath is
advantageous
containing 3 wt.% asMg.
it stabilizes
The surface theappearance
structure of ofthethecoatings
coatingis and reduces
consistent withitsthe
thickness.
results The
thickness
of unitary of theofcoatings
tests obtained
mass changes andin the ZnAl23Mg
confirms baths without
the best corrosion the addition
resistance of coatings of Si was
obtained
much greaterin the and
bathranged
with 3 wt.%
fromMg content.
110–120 µm Increasing
[33]. At thethe Mg
same content
time, to 6 wt.%
both in thelowers
case of the
the corrosion
tested resistance
ZnAl23MgSi of the coating,
coatings but it is still
and ZnAl23Mg better than
coatings [33]the
canresistance
be noticed of the
thatcoating
the addition
obtained
of 3 wt.% in Mg
the Mg-free bath.significantly
to the bath The previous tests
reducesof thethe
corrosion
growthresistance of traditional
of corrosion products. hotOn the
dip galvanizing coating indicate breakthroughs to the substrate,
other hand, higher Mg contents in the bath (6 wt.%) contribute to an increase e.g. breakthroughs to the in the
substrate of approx. Two times thicker coatings took place after 1000 h of exposure in a salt
amount of corrosion products on the surface of the coating, thus lowering its corrosion
chamber [35,36]. Traditional zinc coatings show a unitary weight gain of corrosion products
resistance.
of 140.34 g/m2 for coatings obtained in hot dip galvanizing zinc bath with Bi [35] or even
170.38Figure
g/m2 for9 shows
coatingsthe surface
obtained appearance
in baths containing of the
ZnAl23Si0.4,
total addition ZnAl23AlMg3Si0.4,
of Bi and Sn [36]. and
ZnAl23AlMg6Si0.4
Thus, the corrosion of coatings
the coatingsafter 1500 hbyexposure
obtained batch hotin dipthe salt chamber.
method After baths
in ZnAl23MgSi completion
ofan
in the corrosion containing
environment test, the coatings
chloride did not slower
is much penetrate
than the substrate,
in the which confirms
case of traditional hot-dip their
very high corrosion
galvanizing coatings. resistance. The coating obtained in the ZnAl23Si0.4 bath (Figure 9a)
shows the highest proportion of white corrosion products on the surface. White corrosion
products are identified as zinc or aluminum corrosion products [34]. It is also evident that
more white corrosion products remain on the surface of the coating obtained in the bath
containing 6 wt.% Mg (Figure 9c) than on the surface of the coating obtained in the bath
containing 3 wt.% Mg. The surface appearance of the coatings is consistent with the results
of unitary tests of mass changes and confirms the best corrosion resistance of coatings
obtained in the bath with 3 wt.% Mg content. Increasing the Mg content to 6 wt.% lowers
 the substrate of approx. Two times thicker coatings took place after 1000 h of exposure in
a salt chamber [35,36]. Traditional zinc coatings show a unitary weight gain of corrosion
products of 140.34 g/m2 for coatings obtained in hot dip galvanizing zinc bath with Bi [35]
or even 170.38 g/m2 for coatings obtained in baths containing the total addition of Bi and
Coatings 2022, 12, 1207 Sn [36]. Thus, the corrosion of the coatings obtained by batch hot dip method in 15 of 22
ZnAl23MgSi baths in an environment containing chloride is much slower than in the case
of traditional hot-dip galvanizing coatings.

(a) (b) (c)

Figure 9. The appearance of the surface of research coatings obtained in the: (a) ZnA
ZnAl23AlMg3Si0.4,
(a) and (c) ZnAl23AlMg6Si0.4
(b) bath after 1500
(c) h of exposure in neutr
test.
Figure
Figure9.9.The appearance
The of the
appearance of surface of research
the surface coatings
of research obtained
coatings in the: (a)
obtained in ZnAl23Si0.4, (b).
the: (a) ZnAl23Si0.4,
ZnAl23AlMg3Si0.4, and (c) ZnAl23AlMg6Si0.4 bath after 1500 h of exposure in neutral salt spray
(b) ZnAl23AlMg3Si0.4, and (c) ZnAl23AlMg6Si0.4 bath after 1500 h of exposure in neutral salt
3.3.3.
test.
spray Corrosion resistance in the Sulfur Dioxide Test in a Humid Atmosphere
test.
3.3.3. The corrosion
3.3.3.Corrosion
Corrosionresistance
Resistance
resistance
in the Sulfur
in the
inDioxide
a humid
Dioxide
Sulfur in aatmosphere
TestTest Humid
in
containing
Atmosphere
a Humid Atmosphere
sulfur comp
determined
The
Thecorrosion
corrosioncomparatively
resistance
resistanceinin foratmosphere
a humid
a humid coatings obtained
containing
atmosphere containing insulfur
sulfur ZnAl23MgSi
compounds
compounds baths con
was was
determined
wt.% Si and comparatively for
the reference coatings obtained
coating in ZnAl23MgSi
obtained baths
in thebaths containing
ZnAl23Si0.4 0.4
bath.
determined comparatively for coatings obtained in ZnAl23MgSi containing 0.4 wt.%The ch
wt.% Si and the reference coating obtained in the ZnAl23Si0.4 bath. The change in the
Si and
unitarythe reference
mass coating obtained in the ZnAl23Si0.4 bath. The change in the unitary
unitary mass of theof the ZnAl23MgSi0.4
ZnAl23MgSi0.4 coating
coating during during
exposure exposure
to a humid to acon-
atmosphere humid atmo
mass of the ZnAl23MgSi0.4 coating during exposure to a humid atmosphere containing
taining
taining sulfur
sulfur compounds
compounds is shown inis Figure
shown 10.in Figure 10.
sulfur compounds is shown in Figure 10.

Figure 10. Dependence of unitary changes in the mass of coatings obtained in the research baths
during the sulfur dioxide in a humid atmosphere test.

In the initial period of the corrosion test, up to about 5–7 test cycles, all coatings showed
weight gains. During this time, the highest weight gain was observed for the reference
 Coatings 2022, 12, x FOR PEER REVIEW 16 of 22

Coatings 2022, 12, 1207 Figure 10. Dependence of unitary changes in the mass of coatings obtained in the research baths
16 of 22
during the sulfur dioxide in a humid atmosphere test.

In the initial period of the corrosion test, up to about 5–7 test cycles, all coatings
coating
showed obtained
weight gains. in the ZnAl23Si0.4
During this time,bath. At the weight
the highest same time, the coatings
gain was observedobtained
for the ref- in the
baths
erencecontaining
coating obtainedmagnesiumin theshowed
ZnAl23Si0.4a smaller
bath.unitary mass time,
At the same gain compared
the coatings to obtained
the reference
coating,
in the bathswhich provesmagnesium
containing that fewer showed corrosion products
a smaller accumulate
unitary mass gain oncompared
their surface.
to theAt a
further
reference stage of the
coating, research,
which proves a reduction
that fewerin unitary products
corrosion weight was observedonfor
accumulate all coatings.
their sur-
Based
face. Aton the observed
a further stage ofweight loss, it acan
the research, be concluded
reduction thatweight
in unitary the coating is dissolving.
was observed for all The
coatings.
course ofBased on themass
the unitary observedchange weight
curve loss, it canindicates
clearly be concluded thatreference
that the the coating is dis-
ZnAl23Si0.4
solving. The course of the unitary mass change curve clearly indicates
coating dissolves most intensively. After completion of the corrosion test, the unitary that the reference
ZnAl23Si0.4
mass loss was coating
6.91 ±dissolves
0.28 g/m 2 for
most intensively.
the coating After completion
obtained in theofZnAl23Mg6Si0.4
the corrosion test,bath the and
unitary mass loss2 was 6.91 ± 0.28 g/m 2 for the coating obtained in the ZnAl23Mg6Si0.4
7.72 ± 0.19 g/m for the coating obtained in the ZnAl23Mg3Si0.4 bath, respectively. The
bath unitary
final and 7.72weight± 0.19 g/m
loss2of forthethereference
coating obtained
ZnAl23Si0.4in the ZnAl23Mg3Si0.4
coating was 9.72 ± bath,
0.29 g/m 2 . Thus,
respec-
tively.
the The final
addition of Mgunitary
has aweight
positive losseffect
of theonreference ZnAl23Si0.4
the corrosion coating
resistance was 9.72in± a0.29
of coatings humid
g/m2. Thus, thecontaining
environment addition ofsulfurMg has a positive effect
compounds. on studied
In the the corrosion
rangeresistance of coatings its
of its concentration,
in a humid
high content environment
in the bath containing
of 6 wt.% was sulfurthecompounds.
most effectiveIn the studied range
in reducing of its concen-
the dissolution rate of
tration, its high content in the bath of 6 wt.% was the most effective in reducing
the coating, but with a content of 3 wt.%, the dissolution rate of the coating was only slightly the disso-
lution rate
faster. The of the coating,
obtained resultsbutofwith a content
unitary weight of changes
3 wt.%, the dissolution
of coatings rate of in
obtained theZnAl23MgSi
coating
was only slightly faster. The obtained results of unitary weight changes
baths indicate their much better corrosion resistance compared to traditional zinc coatings. of coatings ob-
tained in ZnAl23MgSi baths indicate their much better corrosion
Corrosion tests conducted in the same environment as traditional zinc coatings showed resistance compared to
traditional zinc coatings. Corrosion tests conducted in the same
their continuous dissolution from the beginning of the test [35,36]. However, after 30 testenvironment as tradi-
tional zinc coatings showed their continuous dissolution from the beginning of the test
cycles, they showed a unitary weight loss of 24.56 g/m2 for coatings obtained in a bath
[35,36]. However, after 30 test cycles, they showed a unitary weight loss of 24.56 g/m2 for
containing the addition of Bi [35] and 27.46 g/m2 for coatings obtained in2baths containing
coatings obtained in a bath containing the addition of Bi [35] and 27.46 g/m for coatings
a total addition of Bi and Sn [36]. Final weight losses of ZnAl23MgSi coatings are more
obtained in baths containing a total addition of Bi and Sn [36]. Final weight losses of
than 3 times smaller compared to traditional zinc coatings, and the initial weight loss
ZnAl23MgSi coatings are more than 3 times smaller compared to traditional zinc coatings,
of corrosion products may additionally delay the coating dissolution processes. After
and the initial weight loss of corrosion products may additionally delay the coating dis-
completion of the corrosion test in a humid atmosphere containing sulfur compounds, no
solution processes. After completion of the corrosion test in a humid atmosphere contain-
penetration of the coating into the substrate was found, and their appearance is gray and
ing sulfur compounds, no penetration of the coating into the substrate was found, and
dull (Figure
their appearance 11). is gray and dull (Figure 11).

(a) (b) (c)

Figure 11.
Figure 11. The
Theappearance of the
appearance surface
of the of research
surface coatings
of research obtained
coatings in the: (a)
obtained ZnAl23Si0.4,
in the: (b).
(a) ZnAl23Si0.4,
ZnAl23AlMg3Si0.4 and (c) ZnAl23AlMg6Si0.4 bath after 30 cycles of exposure in sulfur dioxide test
(b) ZnAl23AlMg3Si0.4 and (c) ZnAl23AlMg6Si0.4 bath after 30 cycles of exposure in sulfur dioxide
in a humid atmosphere.
test in a humid atmosphere.

3.3.4. Corrosion Resistance in the Electrochemical Test

Polarization curves of coatings obtained in ZnAl23MgSi baths and ZnAl23Si0.4 ref-
erence coatings recorded in a 3.5% NaCl solution are shown in Figure 12. The values of
the corrosion current density (jcorr ) were determined using extrapolation of the cathode
and anode branches of the Tafel lines to the corrosion potential (Ecorr ) [37]. The shape of
 Polarization curves of coatings obtained in ZnAl23MgSi baths and ZnAl23Si0
erence coatings recorded in a 3.5% NaCl solution are shown in Figure 12. The va
the corrosion current density (jcorr) were determined using extrapolation of the ca
and anode branches of the Tafel lines to the corrosion potential (Ecorr) [37]. The sh
Coatings 2022, 12, 1207 the polarization curves for the tested coatings shows slight differences,17however, of 22 o
clearly notice a shift of the cathodic and anodic branches of the coatings obtained
containing baths towards lower current density values and a shift of the corrosion
the
tialpolarization
(Ecorr) towards curves for the
more tested coatings
negative values.shows
It canslight differences,
be seen however,
that the lowestone can
corrosion po
clearly notice a shift of the cathodic and anodic branches of the coatings obtained in Mg-
(Ecorr) has coatings obtained in a bath containing 3 wt.% Mg. The corrosion potentia
containing baths towards lower current density values and a shift of the corrosion potential
coating
(E obtained in the Zn23Al3MgSi bath (Table 9) is −865.78 and −862.21 mV (vs.
corr ) towards more negative values. It can be seen that the lowest corrosion potential
respectively,
(E corr ) has coatingswith a value
obtained in aof 0.2containing
bath wt.% and3 wt.%
0.4 wt.% Si in
Mg. The the bath.
corrosion Silicon
potential at the con
of the
coating obtained in the Zn23Al3MgSi bath (Table 9) is − 865.78 and
3 wt.% Mg in the bath does not significantly affect the value of the corrosion po − 862.21 mV (vs. NHE),
respectively, with a value of 0.2 wt.% and 0.4 wt.% Si in the bath. Silicon at the content
(Ecorr). Coatings obtained in a bath containing 6 wt.% Mg showed lower corrosion po
of 3 wt.% Mg in the bath does not significantly affect the value of the corrosion potential
(Ecorr).).Coatings
(E With such Mg content,
obtained the effect6 of
in a bath containing Si content
wt.% Mg showed in lower
the bath on lowering
corrosion potential the cor
corr
potential (E corr) was also observed. The corrosion potential of the
(Ecorr ). With such Mg content, the effect of Si content in the bath on lowering the corrosion coating obtained
Zn23Al6MgSi
potential (Ecorr ) wasbathalso(Table
observed.9) is −902.56
The and
corrosion −915.34
potential mVcoating
of the (vs. NHE),
obtainedrespectively,
in the
Zn23Al6MgSi bath (Table 9) is − 902.56 and − 915.34 mV (vs. NHE),
value of 0.2 wt.% and 0.4 wt.% Si in the bath. A negative value of the corrosion respectively, with a pot
value of 0.2 wt.% and 0.4 wt.% Si in the bath. A negative value of the corrosion potentials
(Ecorr) indicates that these coatings provide sacrificial protection for steel [38], how
(Ecorr ) indicates that these coatings provide sacrificial protection for steel [38], however, a
lowerpotential
lower potential may may
also also indicate
indicate a higher
a higher corrosioncorrosion
tendency of tendency of the coating.
the coating.

Figure 12. Curves of anodic and cathodic polarization of ZnAl23MgSi coatings and the reference
Figure 12. coating
ZnAl23Si0.4 Curvesin of anodic
3.5% and cathodic polarization of ZnAl23MgSi coatings and the re
NaCl solution.
ZnAl23Si0.4 coating in 3.5% NaCl solution.
Table 9. Electrochemical parameters of corrosion of tested coatings in 3.5% NaCl solution.

Table 9. Electrochemical
Type of Coating parameters
Ecorrof corrosion
(mV vs. NHE)of tested coatings in 3.5%2 )NaCl solution.
jcorr (µA/cm
ZnAl23Si0.4 −19.33 3.88
Type of Coating
ZnAl23Mg3Si0.2
Ecorr (mV vs. NHE)
−865.78
jcorr (µA/cm2)
0.97
ZnAl23Si0.4
ZnAl23Mg3Si0.4 −862.21 −19.33 0.903.88
ZnAl23Mg6Si0.2 −902.56 1.17
ZnAl23Mg3Si0.2 −865.78 0.97
ZnAl23Mg6Si0.4 −915.34 1.35
ZnAl23Mg3Si0.4 −862.21 0.90
TheZnAl23Mg6Si0.2 −902.56
coatings obtained in the bath containing Mg in comparison with the reference1.17
coating (ZnAl23Si0.4) also show a lower value of the corrosion current density (jcorr ). The
ZnAl23Mg6Si0.4 −915.34 1.35
lowest value of the corrosion current (jcorr ) has coatings obtained in a bath containing
3 wt.% Mg.coatings
The Silicon inobtained
this bath in
doesthenotbath
significantly
containingaffectMg
thein
value of the corrosion
comparison with the ref
current density (jcorr ), and its specific values were, respectively, 0.97 µA/cm2 for the coating
coating (ZnAl23Si0.4) also show a lower value of the corrosion current density (jco
obtained in the bath containing 0.2 wt.% Si and 0.90 µA/cm2 for a coating obtained in
alowest value of0.4
bath containing the corrosion
wt.% Si (Tablecurrent (jcorr) the
9). Increasing hasMgcoatings
content obtained
in the bathin
to a bath contai
6 wt.%
Coatings 2022, 12, 1207 18 of 22

increases the corrosion current density (jcorr ) to 1.17 µA/cm2 (for 0.2 wt.% Si in bath) and
1.35 µA/cm2 (for 0.4 wt.% Si in bath). The corrosion current density (jcorr ) of the reference
coating (ZnAl23Si0.4) was 3.88 µA/cm. According to Faraday’s law, the corrosion current
density (jcorr ) characterizes the amount of mass loss [39]. Thus, its lower value for coatings
obtained in the Mg-containing bath indicates an increase in their corrosion resistance.
The cause of increased corrosion resistance of coatings obtained in baths containing Al
and Mg additives has not been unequivocally clarified so far. In the literature, many authors
explain the increased corrosion resistance by the formation of beneficial corrosion products
and their transformation. Li et al. [40] claim that there are two main corrosion products on
the surface of coatings obtained in a bath containing Al and Mg additives: simonkolleite
Zn5 (OH)8 Cl2 ·H2 O and smithsonite Zn5 (OH)6 (CO3 )2 . Simonkolleite Zn5 (OH)8 Cl2 ·H2 O has
a very dense and compact structure [41], while smithsonite Zn5 (OH)6 (CO3 )2 is porous
and has poor adhesion to the coating surface [42]. The barrier properties of smithsonite
Zn5 (OH)6 (CO3 )2 are therefore limited. The formation of simonkolleite Zn5 (OH)8 Cl2 ·H2 O
is preferential in the initial stages of corrosion [43]. The further course of the corrosion
process is related to the increase in the concentration of carbonate ions caused by the
dissolution of atmospheric CO2 [44], which leads to the transformation of simonkolleite
Zn5 (OH)8 Cl2 ·H2 O into smithsonite Zn5 (OH)6 (CO3 )2 [41]. The presence of Mg in the
bath causes Mg ions to precipitate preferentially in relation to carbonate ions [45]. The
concentration of carbonate ions in the corrosion products decreases and the conversion
of simonkolleite Zn5 (OH)8 Cl2 ·H2 O into smithsonite Zn5 (OH)6 (CO3 )2 is inhibited. As a
result, the compactness of the corrosion products and their barrier protection are improved.
Tsujimura et al. [8] showed that the introduction of Mg and Al ions to corrosion products
results in their lower solubility and more stable barrier protection. Additionally, the
presence of Si in the bath causes the Al atoms in the diffusion layer of the coating to move
to the surface. It enhances the effect of inhibiting the transformation of simonkolleite
Zn5 (OH)8 Cl2 ·H2 O into smithsonite Zn5 (OH)6 (CO3 )2 [40].
The corrosion process of coatings obtained in baths containing Al additive takes place
preferably in the interdendritic region rich in zinc [46]. The good corrosion resistance of Al
and its alloys is due to the formation of a very adhesive insoluble and a highly passivating
layer of hydrated aluminum oxide Al2 O3 ·3H2 O on its surface [47]. The corrosive potential
of aluminum in the passive state is over 1 V higher than the standard potential of the metal
in the active state (E◦ (Al3+ /Al) = −1.676 V; vs. SHE [48]). In 0.50 mol/dm3 sodium chloride
solution Ecorr aluminum is −0.57 V vs. NHE. In most aqueous solutions, this metal has a sim-
ilar potential value [49]. As a result, in the coating aluminum-rich dendrites are protected
with a passive layer of aluminum oxide, which is chemically inactive in a wide pH range,
has high hardness, and provides barrier protection [50]. Moreover, due to the potential
difference, the zinc-rich interdendritic regions are more anodic (E◦ (Zn2+ /Zn) = −0.7618 V;
vs. SHE [48]) compared to Al-rich dendrites.
The conducted structural tests of ZnAl23MgSi coatings indicate that the addition of
Mg and Si causes the formation of new phases in the coating. Magnesium is also located in
the interdendritic region and is released in the form of the MgZn2 intermetallic phase. This
phase occurs in the form of a Zn/MgZn2 eutectic mixture, or in the form of dense regions
of the MgZn2 intermetallic phase. The MgZn2 intermetallic phase has a strongly anodic
potential (Ecorr = −1.029 V vs. SCE [51]). The MgZn2 intermetallic phase in the coating is
the phase with the lowest potential. This leads to a selective dissolution of the MgZn2 phase
which provides cathodic protection (sacrificial protection) for both Zn-rich interdendritic
regions as well as Al-rich dendrites. The research conducted by Han and Ogle [52] also
proved that the MgZn2 intermetallic phase at the open circuit potential showed a much
lower rate of Zn and Mg dissolution compared to pure metals Zn and Mg. The increased
corrosion resistance is explained by the preferential dissolution of Mg, which leads to the
formation of partially protective ZnO and Zn(OH)2 layers, which inhibit further dissolution
of Mg.
Coatings 2022, 12, 1207 19 of 22

The anodic character is also demonstrated by magnesium silicide Mg2 Si (Ecorr = −1.538 V
vs. SCE [51]). The precipitates of this phase were observed in the coatings obtained in the
ZnAl23Mg6Si0.4 bath. The nature of the electrochemical interaction of Mg2 Si in the coating
is similar to the MgZn2 intermetallic phase. However, the tests carried out showed a
decrease in the resistance of the coatings obtained in the ZnAl23Mg6Si0.4 bath. Ahlatci [53]
showed that the corrosion loss of AlSiMg alloys proceeds through the preferential wear of
the Al matrix adjacent to the primary Mg2 Si precipitates. Gharbi and Birbilis [54] describe
corrosion of the Mg2 Si phase as selective Mg dissolution. As a result, the precipitates are
richer in Si while modifying the potential to more noble values. In the AlMgSi alloys, the
Si precipitations show a cathode nature (Ecorr Si = −170 mV/SCE [51]) in relation to the
matrix of the Al solid solution [55], which favors intercrystalline corrosion of the alloys.
A similar dissolution phenomenon of the Al matrix in contact with Si precipitates was
observed in AlSi coatings in the environment containing chlorides [56]. Mg2 Si, however,
tends to form oxides such as SiO2 and MgO, which protect Mg2 Si particles and reduce
the effectiveness of galvanic connection with the matrix [57]. However, the alternation of
the anodic and cathodic states causes the Mg2 Si to dissolve selectively initially, followed
by the dissolution of the areas around the Si-enriched particles. In particular, high Mg2 Si
precipitations favor pitting corrosion around itself [58]. The formation of Mg2 Si precipitates
in the structure of coatings obtained in ZnAl23Mg6Si0.4 baths may therefore explain the
reduction in corrosion resistance compared to coatings obtained in baths containing a lower
proportion of Mg and Si.
The Mg2 Si or MgZn2 intermetallic phases formed by Mg are strongly anodic compared
to other structural components of the coating. The corrosive potential of MgZn2 is less
sensitive to pH changes in a chloride environment than the Al potential, which provides
sacrificial protection in most corrosive environments. The addition of Mg to a ZnAl bath
that already contains Si could potentially reduce the cathodic effect of Si by producing
more anodic Mg2 Si. The presence of Mg ions may also significantly modify the nature and
morphology of corrosion products of coatings obtained in ZnAl baths.

4. Conclusions
The influence of Mg and Si additives on the microstructure, growth kinetics, and
corrosion resistance of coatings obtained by the double dip method in ZnAl23 baths
was investigated. From the results of these studies, the following main conclusions can
be drawn:
• The addition of Mg and Si to the ZnAl23 bath improved the microstructural uniformity
of the coating. The diffusion layer of the coating is composed of the FeAl3 intermetallic
phase. The structure of the outer layer depends on the content of Mg and Si in the
bath. It consists of dendrites of an Al-rich solid solution. The formation of the MgZn2
intermetallic phase was observed in the Zn-rich interdendritic region. With the content
of 3 wt.% Mg this phase locates in the Zn/MgZn2 eutectic, while with the content of
6 wt.% Mg dense interdendritic regions of the MgZn2 phase were observed. The high
content of Mg and Si (6 wt.% Mg; 0.4 wt.% Si) in the bath leads to the formation of
Mg2 Si phase precipitation in the coating.
• Additions of Mg and Si stabilize the growth kinetics of the coating. The course of the
coating growth kinetics curve is parabolic. The high content of Mg and Si (6 wt.% Mg;
0.4 wt.% Si) in the bath leads to an increase in the thickness of the coating.
• The addition of Mg to the bath improves the corrosion resistance of the coatings.
Corrosion tests carried out in neutral salt spray, a humid atmosphere containing SO2,
and tests of electrochemical parameters of corrosion showed better corrosion resistance
of coatings obtained in a bath with Mg addition compared to the reference coating
obtained in a bath of ZnAl23Si0.4. The increase in corrosion resistance is due to the
presence of the more anodic MgZn2 phase. The high content of Mg and Si (6 wt.% Mg;
0.4 wt.% Si) in the bath may weaken the effect of increased corrosion resistance due to
the formation of precipitates of the Mg2 Si phase.
Coatings 2022, 12, 1207 20 of 22

Funding: This research received external funding from the NCN, Poland, No. N N508 592939.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: Publication supported under the pro-quality rector’s grant of the Silesian
University of Technology, grant number 11/030/RGJ21/1037.
Conflicts of Interest: The author declare no conflict of interest.

References
1. J˛edrzejczyk, D. Effect of High Temperature Oxidation on Structure and Corrosion Resistance of the Zinc Coating Deposited on
Cast Iron. Arch. Metall. Mater. 2012, 57, 145–154. [CrossRef]
2. Šmak, M.; Kubíček, J.; Kala, J.; Podaný, K.; Vanĕrek, J. The Influence of Hot-Dip Galvanizing on the Mechanical Properties of
High-Strength Steels. Materials 2021, 14, 5219. [CrossRef] [PubMed]
3. Suliga, M.; Wartacz, R. The influence of the angle of working part of die on the zinc coating thickness and mechanical properties
of medium carbon steel wires. Arch. Metall. Mater. 2019, 64, 1295–1299.
4. Kriner, S.A.; Niederstein, K. Galvalume sheet: Its production, properties and application. In Proceedings of the 3rd International
Conference on Zinc Coated Steel Sheet, Barcelona, Spain, 7–8 June 1991.
5. Goodwin, F.E. An Update on Galfan. In Proceedings of the 14th International Galvanizing Conference, Munich, Germany,
9–14 June 1985.
6. Tano, K.; Higuchi, S. Development and properties of zinc-aluminum alloy coated steel sheet with high corrosion resistance (Super
Zinc). Nippon Steel Tech. Rep. 1985, 25, 29–37.
7. Tanaka, S.; Honda, K.; Takahashi, A.; Morimoto, Y.; Kurosaki, M.; Shindo, H.; Nishimura, K.; Sugiyama, M. The performance of
Zn-Al-Mg-Si hot-dip galvanized steel sheet. In Proceedings of the 5th International Conference on Zinc and Zinc Alloy Coated
Steel, GALVATECH, Brussels, Belgium, 26–28 June 2001; pp. 153–160.
8. Tsujimura, T.; Komatsu, A.; Andoh, A. Influence of Mg content in coating layer and coating structure on corrosion resistance of
hot-dip Zn-Al-Mg alloy coated steel sheet. In Proceedings of the 5th International Conference on Zinc and Zinc Alloy Coated
Steel, GALVATECH, Brussels, Belgium, 26–28 June 2001; pp. 145–152.
9. Volt, M.; Bleeker, R.; Maalman, T.; van Perlstein, E. MagiZincTM: A new generation of hot-dip galvanized products. In Proceedings
of the Galvanized Steel Sheet Forum, ILZRO and IZA, Duesseldorf, Germany, 30–31 May 2006; pp. 13–24.
10. Marek, A. Hot dip Zn-5Al coatings with improved corrosion resistance of reinforcement steel. Metalurgija 2022, 61, 389–391.
Available online: https://hrcak.srce.hr/265930 (accessed on 4 June 2022).
11. Saternus, M.; Kania, H. Effect of Mg on the Formation of Periodic Layered Structure during Double Batch Hot Dip Process in
Zn-Al Bath. Materials 2021, 14, 1259. [CrossRef]
12. Mendala, J. The influence of Si addition in 55AlZn bath on the coating structures obtained in the batch hot dip metallization. IOP
Conf. Ser. Mater. Sci. Eng. 2011, 22, 012005. [CrossRef]
13. Kania, H. The structure of coatings obtained in a ZnAl23Si bath by the batch hot dip method. Solid State Phenom. 2015, 226, 155–160.
[CrossRef]
14. Kania, H. The Influence of Si Content in Steel on Growth Kinetics and Structure of Hot Dip ZnAl23Si Coatings. Solid State Phenom.
2015, 226, 133–136. [CrossRef]
15. Nowacki, K.; Kania, H.; Wieczorek, J.; Smalcerz, A. The Properties of ZnAlMg Alloys for Batch Hot Dip Metallization. Solid State
Phenom. 2016, 24, 143–148. [CrossRef]
16. ISO 9227:2017; Corrosion Tests In Artificial Atmospheres—Salt Spray Tests; Polish Version PN EN ISO 9227:2017. Polish
Committee for Standardization: Warszawa, Poland, 2017.
17. EN ISO 6988:2000; Metallic and Other Non-Organic Coatings—Sulfur Dioxide Test with General Condensation of Moisture.
Polish Committee for Standardization: Warszawa, Poland, 2000.
18. Liberski, P. Physicochemical Basic of Rational Shaping of Aluminium Dip Coatings on Iron; Silesian University of Technology:
Gliwice, Poland, 2002. (In Polish)
19. Riabov, W.R. Aluminizing of Steel; Oxonian Press: New Delhi, India, 1985.
20. Lainer, D.I.; Kurakin, A.K. Tekhnologiya Legkikh Metallov: Nauch.-Tekhn. Byull. (Technology of Light Alloys: Scientific and Technical
Bulletin); VILS: Moscow, Russia, 1967; p. 72.
21. Selverian, J.H.; Marder, A.R.; Notis, M.R. The effects of silicon on the reaction between solid iron and liquid 55 wt pct Al-Zn baths.
Met. Trans. A 1989, 20, 543–555. [CrossRef]
22. Honda, K.; Ushioda, K.; Yamada, W. Influence of Si Addition to the Coating Bath on the Growth of the Al-Fe Alloy Layer in
Hot-dip Zn-Al-Mg Alloy-coated Steel Sheets. ISIJ Int. 2011, 51, 1895. [CrossRef]
23. Ranjan, M.; Tewari, R.; van Ooij, W.J.; Vasudevan, V.K. Effect of Ternary Additions on the Structure and Properties of Coatings
Produced by a High Aluminum Galvanizing Bath. Metall. Trans. A 2004, 35, 3707–3720. [CrossRef]
Coatings 2022, 12, 1207 21 of 22

24. Perrot, P.; Tissier, J.C.; Dauphin, J.Y. Stable and Metastable Equilibria in the Fe-Zn-Al System at 450 ◦ C. Int. J. Mater. Res. 1992,
83, 786–790. [CrossRef]
25. Peng, H.P.; Su, X.P.; Wang, J.H.; Li, Z. Interface reaction mechanism for galvanizing in Zn-Al baths. Chin. J. Nonferrous. Met. 2012,
22, 3168–3175.
26. McDevitt, E.; Morimoto, Y.; Meshii, M. Characterization of the Fe-Al interfacial layer in a commercial hot-dip galvanized coating.
ISIJ Int. 1997, 37, 776–782. [CrossRef]
27. Horstmann, D. The Course of Reactions between Iron and Molten Zinc Containing Aluminum; Zinc Development Association:
London, UK, 1976.
28. Xie, Y.; Du, A.; Zhao, X.; Ma, R.; Fan, Y.; Cao, X. Effect of Mg on Fe-Al interface structure of hot-dip galvanized Zn-Al-Mg alloy
coatings. Surf. Coat. Technol. 2018, 337, 313–320. [CrossRef]
29. Liu, Y.; Tang, M.; Song, Y.; Wu, Y.; Peng, H.; Su, X.; Wang, J. Reactions of FeCr alloys with liquid zinc in hot-dip galvanizing. Surf.
Coat. Technol. 2015, 276, 714–720. [CrossRef]
30. Gao, L.; Li, Z.; Kuang, X.; Yin, F.; Ji, H. Formation of periodic layered structure during hot-dip galvanizing in Al-Zn-Mg bath.
Surf. Coat. Technol. 2016, 304, 306–315. [CrossRef]
31. Tatarek, A.; Saternus, M. Research on the phenomena of diffusion dissolution of reactive steels in a zinc bath with the addition of
bismuth. Ochr. Przed Koroz. 2018, 7, 186–190. (In Polish)
32. Su, X.; Wu, C.; Liu, D.; Yin, F.; Zhu, Z.; Yang, S. Effect of vanadium on galvanizing Si-containing steels. Surf. Coat. Technol. 2010,
205, 213–218. [CrossRef]
33. Kania, H.; Bierońska, M. Corrosion resistance of coatings obtained in a Zn+23Al bath with Mg additions. Ochr. Przed Koroz. 2013,
10, 445–448.
34. Zhang, X.G. Corrosion and Electrochemistry of Zinc; Springer-Verlag New York Inc.: New York, NY, USA, 2013.
35. Kania, H.; Saternus, M.; Kudláček, J. Impact of Bi and Sn on microstructure and corrosion resistance of zinc coatings obtained in
Zn-AlNi bath. Materials 2020, 13, 3788. [CrossRef] [PubMed]
36. Kania, H.; Saternus, M.; Kudláček, J.; Svoboda, J. Microstructure characterization and corrosion resistance of zinc coating obtained
in a Zn-AlNiBi galvanizing bath. Coatings 2020, 10, 758. [CrossRef]
37. Kelly, R.G.; Scully, J.R.; Shoesmith, D.W.; Buchheit., R.G. Electrochemical Techniques in Corrosion Science and Engineering; Marcel
Dekker, Inc.: New York, NY, USA; Basel, Switzerland, 2003.
38. Dalledone, E.; Barbosa, M.A.; Wolynec, S. Zinc-55% aluminum-1.6% silicon coating compared with zinc coating. Mater. Perform.
1995, 34, 24–28.
39. Kuz, M. Handbook of Environmental Degradation of Materials; William Andrew Publishing, Inc.: Norwich, UK, 2005.
40. Li, S.; Gao, B.; Yina, S.; Tub, G.; Zhub, G.; Sunb, S.; Zhu, X. The effects of RE and Si on the microstructure and corrosion resistance
of Zn-6Al-3Mg hot dip coating. Appl. Surf. Sci. 2015, 357, 2004–2012. [CrossRef]
41. Volovitch, P.; Allely, C.; Ogle, K. Understanding corrosion via corrosion product characterization: I. Case study of the role of Mg
alloying in Zn-Mg coating on steel. Corros. Sci. 2009, 51, 1251–1262. [CrossRef]
42. Komatsu, A.; Izutani, H.; Tsujimura, T.; Andoh, A.; Kittaka, T. Corrosion resistance and protection mechanism of hot-dip
Zn-Al-Mg alloy coated steel sheet under accelerated corrosion environment. Tetsu Hagane 2000, 86, 534–541. [CrossRef]
43. Prosek, T.; Thierry, D.; Taxen, C.; Maixner, J. Effect of cations on corrosion of zinc and carbon steel covered with chloride deposits
under atmospheric conditions. Corros. Sci. 2007, 49, 2676–2693. [CrossRef]
44. Hosking, N.C.; Ström, M.A.; Hhipway, P.H.; Rudd, C.D. Corrosion resistance of zinc–magnesium coated steel. Corros. Sci. 2007,
49, 3669–3695. [CrossRef]
45. Li, S.; Gao, B.; Tu, G.; Hu, L.; Sun, S.; Zhu, G.; Yin, S. Effects of magnesium on the microstructure and corrosion resistance of
Zn-55Al-1.6Si coating. Constr. Build. Mater. 2014, 71, 124–131. [CrossRef]
46. Mendala, J. Influence of the cooling method on the structure of 55AlZn coatings. IOP Conf. Ser. Mater. Sci. Eng. 2011, 22, 012004.
[CrossRef]
47. Rincón, O.; Rincón, A.; Sanchez, M.; Romero, N.; Salas, O.; Delgado, R.; López, B.; Uruchurtu, J.; Marroco, M.; Panosian, Z.
Evaluating Zn, Al and Al-Zn coatings on carbon steel in a special atmosphere. Constr. Build. Mater. 2009, 23, 1465–1471. [CrossRef]
48. Lide, D.R. (Ed.) CRC Handbook of Chemistry and Physics, 90th ed.; Taylor and Francis Group LLC: Boca Raton, FL, USA, 2010.
49. Baszkiewicz, J.; Kamiński, M. Korozja Materiałów; Oficyna Wydawnicza Politechniki Warszawskiej: Warszawa, Poland, 2006.
50. Moffitt, C.E.; Wieliczka, D.M.; Yasuda, H.K. An XPS study of the elemental enrichment on aluminium alloy surfaces from chemical
cleaning. Surf. Coat. Technol. 2002, 137, 188–196. [CrossRef]
51. Birbilis, N.; Buchheit, R.G. Electrochemical Characteristics of Intermetallic Phases in Aluminum Alloys. J. Electrochem. Soc. 2005,
152, B140–B151. [CrossRef]
52. Han, J.; Ogle, K. Dealloying of MgZn2 Intermetallic in Slightly Alkaline Chloride Electrolyte and Its Significance in Corrosion
Resistance. J. Electrochem. Soc. 2017, 164, C952–C961. [CrossRef]
53. Ahlatci, H. Production and corrosion behaviours of the Al-12Si-XMg alloys containing in situ Mg2 Si particles. J. Alloys Compd.
2010, 503, 122–126. [CrossRef]
54. Gharbi, O.; Birbilis, N. Clarifying the Dissolution Mechanisms and Electrochemistry of Mg2 Si as a Function of Solution pH. J.
Electrochem. Soc. 2018, 165, C497–C501. [CrossRef]
Coatings 2022, 12, 1207 22 of 22

55. Zeng, F.; Wei, Z.; Li, C.; Tan, X.; Zhang, Z. Corrosion Mechanism Associated with Mg2 Si and Si Particles in Al-Mg-Si Alloys. Trans.
Nonferrous Met. Soc. China 2011, 21, 2559–2567. [CrossRef]
56. Vu, A.Q.; Vuillemin, B.; Oltra, R.; Allély, C. In Situ Investigation of Sacrificial Behaviour of Hot Dipped AlSi Coating in Sulphate
and Chloride Solutions. Corros. Sci. 2013, 70, 112–118. [CrossRef]
57. Escalera-Lozano, R.; Pech-Canul, M.I.; Pech-Canul, M.A.; Montoya-Dávila, M.; Uribe-Salas, A. The Role of Mg2 Si in the Corrosion
Behavior of Al-Si-Mg Alloys for Pressureless Infiltration. Open Corros. J. 2010, 3, 73–79. [CrossRef]
58. Volovitch, P.; Barrallier, L.; Saikaly, W. Microstructure and Corrosion Resistance of Magnesium Alloy ZE41 with Laser Surface
Cladding by Al-Si Powder. Surf. Coat. Technol. 2008, 202, 4901–4914. [CrossRef]