Materials and Design 30 (2009) 42674272

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Materials and Design

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Mechanical behaviour of ZnFe alloy coated mild steel

C.N. Panagopoulos *, E.P. Georgiou, P.E. Agathocleous, K.I. Giannakopoulos
Laboratory of Physical Metallurgy, National Technical University of Athens, 15780 Zografos, Greece

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

Article history: Zinc alloy coatings containing various amounts of Fe were deposited by electrodeposition technique on a
Received 27 February 2009 mild steel substrate. The concentration of Fe in the produced alloy coatings ranged from 0 to 14 wt.%,
Accepted 20 April 2009 whereas the thickness of the coatings was about 50 lm. Structural and metallurgical characterization
Available online 3 May 2009
of the produced coatings was performed with the aid of X-ray Diffraction (XRD) and Scanning Electron
Microscopy (SEM) techniques. This study aims in investigating the mechanical behaviour of ZnFe coated
Keywords: mild steel specimens, as no research investigation concerning the tensile behaviour of Zn alloy coated fer-
A. Ferrous metals and alloys
rous alloys has been reported in the past. The experimental results indicated that the ultimate tensile
C. Coatings
E. Mechanical
strength of the ZnFe coated mild steel was lower than the bare mild steel. In addition, the ductility of
the ZnFe coated mild steel was found to decrease signicantly with increasing Fe content in the coating.
2009 Elsevier Ltd. All rights reserved.

1. Introduction tion, the friction coefcient of both tribosystems decreased with

It is well known that zinc coatings are used extensively for the
protection of mild steel substrates in various corrosion environ-
ments. However, the increasing and new demanding technological
applications have led to the development of new zinc coatings.
These coatings consist of alternate chemical composition (zinc al-
loy or zinc composite coatings) [14].
Panagopoulos et al. [1] studied the wear behaviour of ZnCo
coatings, with cobalt content ranging from 0 to 4 wt.%, which were
deposited on copper substrates via electrodeposition technique.
These researchers observed that the friction coefcient of the sys-
tem ZnCo coated copper 410 stainless steel was not signicantly
affected by the cobalt concentration (04 wt.%) in the alloy coating,
for the used experimental conditions and cobalt content obtained.
Hosking et al. [2] investigated the corrosion behaviour of Zn
Mg coated mild steel in acidied NaCl solution. They found that
ZnMg alloy coated mild steel exhibited greater corrosion resis-
tance in comparison to a conventional Zn coated mild steel. In both
cases the thickness of the coatings was similar. This improvement
of corrosion resistance was attributed to the formation of corrosion
products (simonkolleite), which hinder the diffusion of halide ions
from the solution to the surface layers of the coated material.
Panagopoulos et al. [3] studied the wear behaviour of Zn
14 wt.% Ni alloy coatings on mild steel against alumina and stain-
less steel counterface materials. These investigators observed that
the friction coefcient of Zn14 wt.% Ni coating alumina was
higher than that of Zn14 wt.% Ni coating stainless steel. In addi-
* Corresponding author. Tel.: +3210 7722171; fax: +3210 7722119.
E-mail address: chpanag@metal.ntua.gr (C.N. Panagopoulos).
increasing applied load.
Praveen and Venkatesha [4] investigated the surface properties
of composite ZnTiO2 coatings electrodeposited on mild steel sub-
strate. The above researchers found that the incorporation of TiO2
nano-particles in the Zn coating has led to an improvement in crys-
tal structure, microhardness, corrosion and wear resistance of the
coating.
De Wit et al. [5] studied the microhardness of ZnFe electrode-
posited coatings, with an iron content ranging from 7 to 45 wt.%.
These investigators observed that the microhardness of the pro-
duced alloy coatings increased considerably with increasing iron
concentration, due to the formation of intermetallic phases.
Drewien et al. [6] investigated the effect of heat treatment tem-
perature on the microstructure of ZnFe alloy coating on mild steel
substrates. The iron concentration ranged from 6 to 13 wt.%. They
observed the following phase transformations: (a) at 150 C, g (Zn
solid solution) ? G phase , (b) at 240 C, G ? f (FeZn13) phase and
(c) at 300 C, G ? d (FeZn7) or C1 (Fe11Zn40) phase.
Panagopoulos et al. [7] investigated the wear behaviour of Zn
Fe alloy coatings, with different iron content (014 wt.%). The fric-
tion coefcient of the tribosystem ZnFe alloy coatings 410 stain-
less steel was observed to decrease with increasing iron content in
the alloy coating. The dominant wear mechanisms of the above
coatings were observed to be extensive plastic deformation and
shearing of the coating, due to the ploughing action of the harder
steel spheres.
This research investigation aims in providing a thorough study
of the mechanical behaviour of ZnFe alloy coated mild steel, with
various iron content (014 wt.%). It should be noted that, although
ZnFe alloy coatings have been used in various technological and
industrial applications, no research investigation concerning the

0261-3069/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2009.04.026
4268 C.N. Panagopoulos et al. / Materials and Design 30 (2009) 42674272

tensile behaviour of Zn electrodeposited coatings on ferrous alloys vation in DRECA solution (10% HCl solution containing hexameth-
has been reported. ylenetetramine inhibitor).
ZnFe alloy coatings were deposited, from a sulphate solution
2. Experimental (Table 2), on the mild steel substrates by using a constant current
electrodeposition technique. Cathode was the mild steel substrate,
The substrate material used in this study was a commercial whereas the anode was a platinum electrode. The composition of
supplied mild steel alloy sheet. The chemical composition and the electrodeposition bath and the deposition parameters are given
mechanical properties of the examined mild steel are presented in Table 2. Magnetic agitation was conducted at 200 rpm. The mild
in Table 1. Mild steel substrates with length 40 mm, width steel substrate and the platinum anode were placed vertically, fac-
20 mm and thickness 0.5 mm were produced for the structural ing each other. The in-between distance was approximately
study and microhardness experiments, whereas standard tensile 10 mm. In addition, for the production of zinc alloy coated tensile
specimens were prepared for the tensile experiments. These spec- specimens, platinum anodes having dimensions 10 cm length,
imens were machined to an average roughness of 0.9 lm and then 2 cm width and 0.1 mm width were used.
annealed at 550 C for 2 h in an Ar-inert atmosphere. The annealing ZnFe coatings with different Fe content, from 0 to 14 wt.% and
process was followed by alkaline cleaning of the specimens in a 50 lm thickness were studied in this work. The surface and the
0.2 M NaOH solution at 70 C, rinsing by deionised water and acti- cross-sections of the coatings were studied with the aid of a JEOL
6100 Scanning Electron Microscope (SEM). The chemical composi-
tion of the produced coatings was examined with the aid of an
Table 1 NORAN TS 5500 Electron Dispersive Spectrometer (EDS), which
Characterization of mil steel substrate. was connected to the SEM. With the aid of a SIEMENS D5000 X-
Chemical composition 99.43% Fe, 0.07% C, 0.02% Si, 0.36% Mn, 0.01% P, 0.01% S, ray diffractometer, giving a CuKa radiation from a graphite mono-
(wt.%) 0.01% Cu, 0.01% Cu, 0.04% Al, 0.02% Cr, 0.02% Ni chromator, the crystal structure of the grown coatings was studied.
Hardness (HVN) 150 The microhardness of the ZnFe alloy coatings was examined in
Ultimate tensile 280 the cross section with the help of a SHIMADZU HMV 2000 microh-
strength (MPa)
Elongation (%) 35
ardness tester, imposing 0.15 N for 15 s.
Yield strength (MPa) 240 The tensile behaviour of the mild steel substrates with ZnFe al-
loy coating, having various Fe concentrations (014 wt.%) and

Table 2
Chemical composition and deposition parameters of Zn and ZnFe.

Zn coating Zn1.8%Fe coating Zn6%Fe coating Zn14%Fe coating

ZnSO47H20 (g/ml) 400 219 110 55
AlCl3 (g/ml) 25
Na2SO4 (g/ml) 75 141 141 141
FeSO42H2O (g/ml) 236 355 414
CuSO4 (g/ml) 0.1 0.05 0.05
Deposition time (min) 30 30 30 30
Current density (mA/cm2) 40 40 40 40
Temperature (C) 30 30 30 30

Fig. 1. Surface morphology of: (a) Zn coating, (b) Zn1.8%Fe alloy coating, (c) Zn6%Fe alloy coating and (d) Zn14%Fe alloy coating.
 C.N. Panagopoulos et al. / Materials and Design 30 (2009) 42674272 4269

50 lm thickness, was studied with the aid of an INSTRON 4482 Table 3

testing system. All tensile experiments were performed at a strain Microhardness values of the produced Zn and ZnFe alloy coatings.

rate of 1.1  103 s1, in laboratory air at room temperature. Hardness (HVN)
Extensive metallurgical microscopy was performed on the surface Mild steel 150
of ZnFe coated steel specimens after applying various values of Zn coating 56
tensile elongation. For each set of experimental conditions, ve Zn1.8%Fe coating 75
independent tests were carried out. Zn6%Fe coating 100
Zn14%Fe coating 203

3. Results and discussion

The surface of ZnFe electrodeposits, with different iron con-

tent, showed a typical nodular structure, Fig. 1ad. For the used
experimental conditions and iron content obtained, the size of
nodulus is seen to increase with increasing iron content. In addi-
tion, it is easily seen that the average roughness of the alloy coating
on mild steel also increased with increasing iron content in the
coating. By examining the cross section of the ZnFe coated mild
steel specimens, it was observed that all coatings were free of
pores or cracks, especially at the interface of electrodeposited alloy
coating with mild steel. This observation is indicative of good
adhesion between the coating and the substrate. The average
thickness of the studied alloy coatings was calculated by using Im-
age Analyzer Programme and was found to be approximately
50 lm.
From the X-ray diffraction spectra, Fig. 2, it was found that:

 The Zn1.8%Fe alloy coating consisted of: (a) iron in zinc solid
solution (g) and (b) FeZn7 intermetallic phase (d).
 The Zn6%Fe alloy coating and the Zn14%Fe alloy coating con- Fig. 3. Engineering stressstrain curves for: (a) bare mild steel, (b) Zn coated mild
steel, (c) Zn1.8%Fe coated mild steel, (d) Zn6%Fe coated mild steel and (e) Zn
sisted of: (a) iron in zinc solid solution (g), (b) FeZn7 intermetal-
14%Fe coated mild steel.
lic phase (d) and (c) Fe4Zn9 intermetallic phase (C).

It can be seen that, the above experimental results are not in full deposition of zinc alloy coatings, a thin Zn(OH)2 lm is formed at
agreement with the zinciron equilibrium phase diagram [8]. the interface between the cathode and the solution. The formation
Explanation for this observation has been given by various investi- of this lm is attributed to localised increase in the pH of the solu-
gators [911]. According to these investigators, during the electro- tion. This lm is believed to hinder the co-deposition of the alloy

Fig. 2. XRD spectrograms of (a) Zn1.8%Fe alloy coated mild steel and (b) Zn14%Fe alloy coated mild steel.
4270 C.N. Panagopoulos et al. / Materials and Design 30 (2009) 42674272
components and increase the deposition rate of zinc on the
substrate.
The average microhardness values of the produced Zn and Zn
Fe alloy coatings are presented in Table 3. In this table the microh-
ardness of the produced coatings is shown to increase signicantly
with increasing iron content in the alloy coating. The higher
microhardness values could be attributed to the increased concen-
tration of hard intermetallic phases d and C per coatings volume,
as observed by X-ray diffraction measurements. This increase is be-
lieved to contribute to the dislocation pinning mechanisms, ob-
served during the interaction of moving dislocations with
existing intermetallic phases. Thus dislocation movement and
multiplication are hindered and the microhardness of the coating
is enhanced. It should be also taken into account that during the
electrodeposition of metallic coatings, hydrogen diffusion from
the solution to the surface layers of the coating takes place [12].
Fig. 4. Metallurgical micrographs of the surface adjacent (1 cm) to the fracture of:
(a) Zn1.8%Fe alloy coating, (b) Zn6%Fe alloy coating and (c) Zn14%Fe alloy
coating.
It has been proved that solute hydrogen atoms often act as disloca-
tion pinning sites, which increase the surface hardness of the
metallic materials [13].
Fig. 3 shows the engineering stressstrain curves for the bare
mild steel specimen in comparison to Zn and ZnFe (with various
Fe content) coated mild steel specimens. From this gure, it can be
observed that the Zn and ZnFe alloy coated steel specimen had
signicantly lower mechanical strength than the bare steel speci-
men. However, the coated specimens had similar ultimate tensile
strength (UTS). It has been found [14] that the ultimate tensile
strength (UTS) of a composite laminate material can be given by
the following equation:
Pt Ps V s Pc V c 1
where Pt is the UTS of the laminate material, Ps is the UTS of the
substrate (mild steel), Pc is the UTS of the coating (zinc alloy coat-
ing) and Vs and Vc are the percentage volume of the substrate and
coating respectively, when compared to the total volume of the
laminate material. In addition, it is widely known that the yield
point (Re) of metallic materials can be related to their hardness
(HV) by the experimental equation [15]:
HV  2:9Re 2
Therefore, by taking into consideration Eqs. (1) and (2) and the
microhardness values given previously (Table 2), it could be said
that the deposition of Zn and ZnFe alloy coatings on the mild steel
substrate will possibly lead to lower UTS values, when compared to
those of bare mild steel. However, for the examined experimental
conditions, the increase of iron content in the alloy coating did
not seem to affect the UTS strength of the laminate material (coat-
ing/mild steel), despite the fact that the average microhardness of
the coating was found to increase with increasing iron content.
From Fig. 3 it could also be said that the ductility of Zn alloy
coated mild steel was found to be lower than the ductility of bare
mild steel. The above observation can be attributed to the fact that
the presence of surface layers blocks the egress of dislocations
from the metallic substrate to the surface layer [16]. Thus, the low-
er the movement and multiplication of dislocation in the bulk sub-
strate results in the decrease of ductility of the coated specimen.
Another observation that could be made from Fig. 3 is that the duc-
tility of ZnFe alloy coatings decreased with increasing iron con-
tent. This phenomenon might be due to the increased presence
of intermetallic phases (d and C) in the coating. These brittle
phases are believed to hinder the egress of dislocations from the
substrate to the coating during the tensile deformation of the
coated specimen via dislocation pinning mechanisms. The de-
125 15
Number of Cracks per Coatings
Width of Coatings Cracks (m)
100
Length (cm-1)
10
75
50
5
25
0 0
0 5 10 15 20
Fe Content (wt. %)
Fig. 5. Comparative graph of the effect of Fe content in the Zn alloy coating on the
number and width of cracks formed on the surface of the coating adjacent (1 cm) to
the fracture area.
 C.N. Panagopoulos et al. / Materials and Design 30 (2009) 42674272 4271

creased movement of dislocation brings about a decrease in the 125 15

Width of Coatings Cracks (m)

ductility of the coated specimen.

Number of Cracks per Coatings

Fig. 4ac present the number of the cracks formed adjacent to
100
the fracture surface (1 cm) of the Zn1.8%Fe, Zn6%Fe and Zn
14%Fe coated mild steel specimens, after tensile testing. By exam- 10

Length (cm-1)
ining the above gures it could be said that, all coatings and espe- 75
cially the Zn14%Fe coated mild steel specimen are heavily
cracked. In the last specimens the number and width of the cracks
50
is much higher than the width of the cracks which appeared in the 5
rst two specimens, Fig. 5. This observation is attributed to the
higher concentration of brittle intermetallic phases in the alloy 25
coating. A point that must be also made is that the cracks formed
in all Zn alloy coatings were observed to be nearly perpendicular
0 0
to the tensile axis. 0 5 10 15
A number of tensile tests were also conducted for the Zn14%Fe Applied Strain (%)
coated mild steel specimens, in order to study the appearance of
surface cracks with increasing applied strain on the laminate mate- Fig. 7. Comparative graph of the effect of applied strain on the number and width of
cracks formed in the center of surface of Zn14%Fe alloy coating.

rial. Fig. 6ac show the density of cracks formed in the center of the
coatings surface, for applied strains of 2%, 7% and 12%, respectively.
By comparing these gures it could be said that the increase in ap-
plied strain during tensile testing has led to an increase in number
and size of surface cracks formed on the surface of the alloy coated
specimen, Fig. 7. The higher crack densities acquired with increas-
ing applied strain values are attributed to the difference ability for
deformation between the substrate and the coating [17]. An
approximate calculation of the number of cracks per coatings
length and the width of cracks as a function of applied strain is pre-
sented in Fig. 7.

4. Conclusions

In this work, the mechanical behaviour of ZnFe alloy coated

mild steel was studied. The main conclusions are the following:

1. The microhardness of the ZnFe coatings on mild steel was

found to increase with increasing iron concentration.
2. The ultimate tensile strength (UTS) of Zn and ZnFe alloy coated
mild steel was lower than that of bare mild steel specimen. For
the experimental conditions studied the UTS was found to be
independent of the iron concentration in the examined
material.
3. The ductility of Zn and ZnFe alloy coated mild steel was lower
than that of bare mild steel specimen. The ductility of the Zn
alloy coated specimens was also found to decrease with
increasing iron content in the coating.
4. The density and width of cracks adjacent to the fracture surface
(1 cm) was found to increase with increasing iron content in the
alloy coating. These cracks were observed to be perpendicular
to the tensile direction.
5. The density and width of cracks in the center of Zn14%Fe coat-
ings surface was found to increase with applied strain.

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