materials

Article
Influence of the Manufacturing Process on Defects in
the Galvanized Coating of High Carbon Steel Wires
Marcello Gelfi 1, *, Luigi Solazzi 1 and Sandro Poli 2
1 Department of Mechanical and Industrial Engineering, Università degli Studi di Brescia, Via Branze 38,
25123 Brescia, Italy; luigi.solazzi@unibs.it
2 IFP SpA, Via Predalva, 25050 Pian Camuno, Italy; poli@ifpwire.it
* Correspondence: marcello.gelfi@unibs.it; Tel.: +39-349-7201440

Academic Editor: Jung Ho Je

Received: 10 January 2017; Accepted: 28 February 2017; Published: 6 March 2017

Abstract: This study is a detailed failure analysis of galvanized high carbon steel wires, which
developed coating cracks during the torsion test performed as a quality control at the end of the
manufacturing process. Careful visual inspections showed that the cracks are already present in the
coating before the torsion test. In order to explain the origin of these cracks, systematic metallographic
investigations were performed by means of optical and scanning electron microscope on both the
wires and the rods that have been cold drawn to produce the wire. The chemical composition of the
galvanized coatings was evaluated by means of energy dispersive spectroscopy. Micro bidimensional
X-ray diffraction experiments were also performed to measure the residual stresses in the galvanized
coating. The results showed that the failure is related to two main factors: the relatively high content
of silicon in the steel and the unsuitable cooling rate of the rods at the exit from the galvanizing
bath. The mechanism proposed to explain the origin of the defects was supported by Finite Elements
Methods simulations and verified with in-plant tests. The proper countermeasures were then applied
and the problem successfully solved.

Keywords: hot-dip galvanizing; high carbon steel wire; cold drawing; defects; FEM; SEM; XRD

1. Introduction
The manufacturing process of galvanized high carbon steel wires starts from the hot-rolled steel
rods, which are austenitized in a furnace and then maintained in a lead bath at a temperature in
the range of 520–560 ◦ C. The soaking time in the bath is long enough to promote the isothermal
transformation of austenite into a fine pearlitic microstructure, the so-called “patented microstructure”,
which is ideal for the following cold drawing operations [1]. The lead particles remaining attached
to the rod surface are removed by acid pickling, which is also a necessary surface pre-treatment for
the following hot-dip galvanizing step. Before the immersion in the molten zinc bath, the steel rod is
fluxed in an aqueous solution containing chloride salts to avoid any surface oxidation. The steel rod
is then maintained in contact with the molten zinc at around 440–460 ◦ C for a few minutes to form
the galvanized coating on its surface [2]. At the exit from the molten zinc bath, the inert gas wiping
dies accurately control the thickness of coating on the surface by removing the excess of molten zinc.
Then the steel rod is spray quenched with a mixture of air and water to obtain a bright shiny finish [3]
(Figure 1).
The zinc coating increases the corrosion resistance of the steel substrate [4] and it is a good solid
lubricant to minimize the friction during the cold drawing process [5]. This process involves pulling
the rod through a series of dies, with the diameter progressively reducing in size. At the exit of the last
die, a small diameter wire (<5 mm) is produced with enhanced tensile strength properties due to the
intense work hardening.

Materials 2017, 10, 264; doi:10.3390/ma10030264 www.mdpi.com/journal/materials

Materials 2017, 10, 264 2 of 12
Materials 2017, 10, 264 2 of 12

The
Theas-fabricated galvanized
as-fabricated galvanizedsteel
steelwire
wireneeds
needstotopass
passa anumber
numberofofquality
qualitytests
testsbefore
beforegoing
goingon
onthe
market, concerning mechanical and corrosion properties. One of these is the torsion test
the market, concerning mechanical and corrosion properties. One of these is the torsion test that that consists
of consists
countingofthe number
counting theofnumber
turns that the wire
of turns canwire
that the sustain
can before
sustainfailure.
before failure.
Materials 2017, 10, 264 2 of 12

The as-fabricated galvanized steel wire needs to pass a number of quality tests before going on
the market, concerning mechanical and corrosion properties. One of these is the torsion test that
consists of counting the number of turns that the wire can sustain before failure.

Figure1.1.Schematic
Figure Schematicsketch
sketch of
of aa continuous
continuous galvanizing
galvanizingprocess
processfor
forwires
wiresand
androds.
rods.

In the present case, as reported by plant operators, the wire produced with specific steel batches
at In
thethe present
end case,
of theFigure
torsionasSchematic
1. reported
test showed by plant
sketch ofthe operators,
formation
a continuous theseveral
of
galvanizing wire produced
processcircumferential with
for wires and specific
rods.cracks, steel batches
randomly
at distributed
the end ofalong the torsion test showed the formation of several circumferential
the circumference and length (Figure 2). A preliminary analysis showed that these cracks, randomly
cracks areIn
distributed the present
along
limitedthe to case,
the as Znreported
circumference layers,andby plant operators,
length
suggesting that the
(Figure thewire
2). produced
Acoating
preliminary couldwith specific
analysis
have somesteelproblems
showedbatches
that these
of
cracks at the end
are limited of the torsion
to thebrittleness. test showed the formation of several circumferential
Zn layers, suggesting that the coating could have some problems of adhesion cracks, randomly
adhesion or excessive
distributed along the circumference and length (Figure 2). A preliminary analysis showed that these
or excessive brittleness.
In literature, the studies concerning the defects in galvanized coatings are mainly related to
cracks are limited to the Zn layers, suggesting that the coating could have some problems of
In adhesion
problemsliterature, the
of delamination,studies
or excessive alsoconcerning
brittleness.named “peeling the defectsoff” or in “shaving”
galvanized of coatings
zinc coating,are mainly related to
which happens
during the
problems forming
literature, operations.
ofIndelamination, also named
the studies The main
concerning“peeling reasons
the off”that
defects can produce
orgalvanized
in “shaving” thisare
of zinc
coatings type
coating,of defect
mainly whichare
related the
happens
to
excessive
during the plastic
forming
problems deformations
operations. The
of delamination, [6],named
also the abnormal
main reasons
“peelingthat growth
off” can of a brittle
produce
or “shaving” this
of zeta
zinctypephase in
of defect
coating, theare
which coating [7,8],
the excessive
happens
the presence
plastic during the
deformations of forming
Mn[6],oxide
the formed The
operations.
abnormal ongrowth
the surface
main reasons ofthat
of a brittle thezeta
cansteel substrate
produce
phase inthis during
thetype annealing
of defect
coating [7,8],are
thethebefore
presence
excessive
galvanizing plastic deformations [6], the abnormal growth of a brittle zeta phase in the coating [7,8],
[9,10].
of Mn oxide formed on the surface of the steel substrate during annealing before galvanizing [9,10].
theinvestigate
presence of Mnpresent oxide formed on the surface ofmetallographic
the steel substrate during annealing before
ToTo investigate thethe
galvanizing [9,10].
present problem, problem, systematic
systematic investigations
metallographic investigations wereperformed
were performed on
on rods
steel steeland rodswiresandbywires
optical by(OM)optical
and (OM)
scanning and scanning electron microscope (SEM). Micro
To investigate the present problem, systematicelectron microscope
metallographic (SEM). were
investigations Micro bidimensional
performed
bidimensional X-ray diffraction experiments 2 (μXRD2) were also carried out to measure the residual
X-ray diffraction
on steel rods experiments
and wires (µXRD by optical ) were(OM)also andcarried
scanning outelectron
to measure the residual
microscope stress in the
(SEM). Micro
stressbidimensional
in the coatings. X-ray Adiffraction
failure mechanism
experiments has been
(μXRD proposed
2) were alsobasealso on
carried outthe base of the
to measure Finite Elements
residual
coatings. A failure mechanism has been proposed also on the of Finite Elements Methods (FEM)
Methodsstress(FEM)
in the simulations
coatings. A that
failure are normally
mechanism hasused
been to model
proposed thermo-mechanical
also on the base of processes
Finite Elements[11,12]
simulations that are normally used to model thermo-mechanical processes [11,12] and verified with
and verified
Methodswith (FEM)in-plant tests.that are normally used to model thermo-mechanical processes [11,12]
simulations
in-plant tests.
Proper countermeasures
and verified with in-plant tests.have been adopted in the plant to solve the problem.
ProperProper
countermeasures
countermeasures have been
have beenadopted
adopted in in the planttoto
the plant solve
solve thethe problem.
problem.

Figure 2. Circumferential cracks on steel wire after the torsion test.

Figure2.2.Circumferential
Figure Circumferential cracks on steel
cracks on steelwire
wireafter
afterthe
thetorsion
torsiontest.
test.
Materials 2017, 10, 264 3 of 12

2. Experimental Procedure

2.1. Materials
The visual inspections of the wires belonging to the failed batch revealed the presence of fine
circumferential cracks in the zinc coating also before the torsion test was performed. These cracks
are difficult to detect by the naked eye, but they became evident when the torsion test is performed
because they are enlarged by the applied shear stresses. To understand if the cracks are a consequence
of the cold drawing process or if they come from the galvanized rod, both the wire and the rod have
been analyzed.
The rods and wires considered in the work are made in C82D steel, according to the EN ISO
16120-2:2011 standard [13]. In particular, two different batches have been analyzed:

- Steel 1: C82D carbon steel rods and wires that failed during the torsion test;
- Steel 2: C82D carbon steel rods and wires that had no cracks.

The steel compositions of the two batches are shown in Table 1. All elements fit with the nominal
ranges prescribed by the EN ISO 16120-2:2011 standard for the C82D steel. In both cases, the rod and
the wire have a diameter of 7 mm and 4.5 mm respectively.

Table 1. Chemical composition (wt. %) of steel batches: Steel 1 (failed) and Steel 2 (good).

Steel %C %Si %Mn %S %P %Cu %Ni %Cr Fe

EN ISO 16120-2 0.80–0.85 0.10–0.30 0.50–0.80 <0.030 <0.030 <0.25 <0.20 <0.15 Balance
Steel 1 0.81 0.215 0.705 0.004 0.015 0.053 0.022 0.03 Balance
Steel 2 0.827 0.188 0.663 0.008 0.01 0.022 0.019 0.032 Balance

The main parameters of the hot-dip galvanizing process are reported in Table 2.

Table 2. Hot-dip galvanizing process parameters.

Process Parameter Value

Rod preheating temperature 160 ◦ C
Molten zinc bath temperature 450 ◦ C
Immersion time ∼
=10 s
Nominal bath composition Zn 99.995%

2.2. Metallographic, Chemical and Residual Stress Analysis

Metallographic analyses were carried out on longitudinal and transversal cross sections cut from
the rods and the wires in different positions. Samples were polished and etched with 2% Nital to
reveal the microstructure of both coating and steel. The microstructures were examined using a LEO
EVO-40XVP scanning electron microscope (Carl Zeiss Microscopy GmbH, Oberkochen, Germany).
Semi-quantitative chemical analyses by the Link Analytical eXL microprobe (EDS) (Oxford Instruments
NanoAnalysis, Buckingamshire, UK) were also carried out.
The residual stress of the rods’ coating was evaluated by means of a D/max-RAPID Rigaku
microdiffractometer (Rigaku Americas Corporation, The Woodlands, TX, USA) equipped with
a cylindrical imaging plate (IP) detector by applying the DRAST method, which is based on a modified
d-sin2 ψ approach [14]. This system is suitable for performing residual stress measurements on
metallic components with a relatively small size and/or a curved geometry [15], as in this case.
Measurements were performed by using a beam collimator of 300 µm at a fixed incidence angle of
20◦ . The voltage and the current were set at 40 kV and 30 mA respectively, with an acquisition time of
1 h. The measurements were performed in the longitudinal direction by using the CuKα radiation.
The residual stress was calculated for the outer eta layer by evaluating the distortion of the (101) Debye
Materials 2017, 10, 264 4 of 12

ring that is the strongest in this crystal lattice. The elastic constants of the eta bulk have been used for
Materials
stress 2017, 10, 264 E = 75 GPa and ν = 0.30 [16].
calculations: 4 of 12

2.3. FEM Simulation of the Defect

Numerical analysis by by Finite
Finite Elements
Elements Method
Method was wasapplied
appliedtotosimulate
simulatethe thedrawing
drawingofofa
agalvanized
galvanized steel
steelwire. InIn
wire. particular,
particular,a small
a smalldefect
defect was
was considered
considered to to
bebepresent
presentin in
thethe
ZnZn coating, in
coating,
order
in order to to
study
study the
thedeformation
deformationofofbothbothcoating
coatingand andsteel
steelbulk
bulkin inthe
the flawed
flawed area.
area. The
The aim of thisthis
simulation was
simulation wasnot not
to to reproduce
reproduce in detail
in detail the whole
the whole cold drawing
cold drawing process, process,
but just tobut
have just to have
qualitative
qualitative information
information about
about the trend the flawed
of the trend of thetoflawed
area assumeareathe to assume
final defect the final defect
morphology, i.e.,morphology,
the bulging
i.e.,the
of thesteel
bulging of the For
substrate. steelthis
substrate.
reason,For this reason,
a single step ofadeformation
single step ofhas deformation has been considered.
been considered.
model geometry
The model geometry defined
defined for
for the
the simulation
simulation isis shownshown in in Figure
Figure 3.3. On the basis of
metallographic analysis,
metallographic analysis,thethe
ZnZn coating
coating thickness
thickness was at
was fixed fixed
40 µm,at while
40 μm, thewhile
defect the
was defect was
considered
considered
to be a coating to be a coating delamination
delamination with the lengthwithofthe100length
µm. Theof 100 μm. The
approach approach
angle of the angle
die is of10◦the
anddiethe
is
10° and
area the area
reduction perreduction
drawing per passdrawing
is 20%. pass is 20%. The
The interface interface
between the between
wire andthe thewire
zinc and the was
coating zinc
coating was
bounded, bounded,
while the zinc while
coating the
andzinc
the coating and are
die surfaces theindie surfaces
contact. Theare in contact.
friction Thebetween
coefficient friction
coefficient
the galvanizedbetween the the
rod and galvanized
die wallrodwasand the die wall
reasonably fixedwas reasonably
at 0.1 [17]. fixed at 0.1 [17].

Figure 3.
Figure 3. Model
Model geometry
geometry for
for FEM
FEM analysis.
analysis.

The numerical analyses were performed by Autodesk Simulation® software software (Software
The numerical analyses were performed by Autodesk Simulation® software software (Software
Release 2016, Autodesk Inc., San Rafael, CA, USA) and the FEM model used the axial-symmetry of
Release 2016, Autodesk Inc., San Rafael, CA, USA) and the FEM model used the axial-symmetry of
the problem. The model is composed of about 700 thousand quadratic axial-symmetry elements. It is
the problem. The model is composed of about 700 thousand quadratic axial-symmetry elements. It is
important to underline that the mesh is not uniform but the size of the elements is very small near
important to underline that the mesh is not uniform but the size of the elements is very small near
the defect. In particular, in that zone, four rows of elements were created along the thickness of the
the defect. In particular, in that zone, four rows of elements were created along the thickness of the
zinc coating. A linear elastic model was considered to simulate the materials. The Young’s modulus,
zinc coating. A linear elastic model was considered to simulate the materials. The Young’s modulus,
shear modulus and Poisson’s ratio of the steel substrate were taken to be 210 GPa, 81 GPa and 0.30
shear modulus and Poisson’s ratio of the steel substrate were taken to be 210 GPa, 81 GPa and 0.30
respectively, those of the coating layer were taken to be 140 GPa, 54 GPa and 0.30 [18]. The yield
respectively, those of the coating layer were taken to be 140 GPa, 54 GPa and 0.30 [18]. The yield
strength of steel was fixed at 1300 MPa considering an average strain hardening of 28% [19], while
strength of steel was fixed at 1300 MPa considering an average strain hardening of 28% [19], while the
the yield strength of the coating was fixed at 130 MPa [18].
yield strength of the coating was fixed at 130 MPa [18].
This is a complex problem due to the nonlinear behavior of materials and because different
This is a complex problem due to the nonlinear behavior of materials and because different surface
surface contact conditions have to be considered in the cracked area. For this aspect, many different
contact conditions have to be considered in the cracked area. For this aspect, many different numerical
numerical analyses were performed in order to evaluate both stress and strain in the wire and in the
analyses were performed in order to evaluate both stress and strain in the wire and in the coating and
coating and to evaluate the deformation of the wire in the area not covered by the zinc layer.
to evaluate the deformation of the wire in the area not covered by the zinc layer.
Materials 2017, 10, 264 5 of 12
Materials 2017, 10, 264 5 of 12

3. Results
3. Results and
and Discussion
Discussion
The metallographic
The metallographicanalysis
analysisstarted
startedconsidering
considering thethe
transversal
transversal sections
sectionsof wires mademade
of wires with Steel
with
1Steel
and12and(Figure 4). The images, collected by SEM in backscattering mode at
2 (Figure 4). The images, collected by SEM in backscattering mode at low magnification, low magnification, show
the zinc-rich
show coating
the zinc-rich as a thin
coating white
as a thin layer
white on the
layer on thegrey steel
grey steelsubstrate.
substrate.InInboth
bothcases,
cases,itit is
is evident
evident
the thickness
that the thicknessof ofthe
thezinc
zinclayer
layerisisnot
notuniform
uniformalong along thethe circumference.
circumference. ThisThis is probably
is probably duedue to
to an
an excess of molten zinc that remained attached on the rod surface at the exit
excess of molten zinc that remained attached on the rod surface at the exit from the galvanizing bath. from the galvanizing
bath.analysis
The The analysis
of rodof rod
crosscross sections
sections showed
showed thethe sameuneven
same unevencoating
coatingthickness,
thickness, confirming
confirming this
hypothesis. It is interesting to observe that in the failed wire, the defects are
interesting to observe that in the failed wire, the defects are located only located only in in
one part
one of
part
the cross section, where the coating is thinner (Figure
of the cross section, where the coating is thinner (Figure 4a). 4a).
The metallographic analysis
analysis was then focused on the failed batch. batch. Longitudinal sections were
cut from both the Steel 1 wire and rod and etched by Nital2 Nital2 to to reveal
reveal thethe coating
coating microstructure.
microstructure.
SEM images were collected in back-scattering mode and reported in Figures 5 and 6. Three layers
can be clearly detected based on their iron content, measured by means of the EDS microprobe: eta
(almost pure zinc), zeta (5%–6% wt. Fe) and delta (7%–11.5% wt. Fe) phase [2]. The gamma phase is
also present
present asas aa very
verythin
thinlayer
layeratatthe
theinterface
interfacewithwiththethesubstrate.
substrate.InInany anycase,
case, the lateral
the resolution
lateral resolution of
the EDS microprobe is not high enough to identify this phase separately
of the EDS microprobe is not high enough to identify this phase separately from the others. from the others.
Figure 5a 5ashows
showsthe thelongitudinal
longitudinal cross section
cross of aof
section defect responsible
a defect for thefor
responsible macroscopic failure
the macroscopic
of the wire
failure during
of the wire the torsion
during the test. It consists
torsion of the local
test. It consists delamination
of the of the Znofcoating,
local delamination the Zn which
coating,is
missing for a length of about 100 µm. The steel substrate in the delaminated
which is missing for a length of about 100 μm. The steel substrate in the delaminated area is not flat area is not flat but it
shows
but a microscopic
it shows bulging.
a microscopic bulging.
The residual zinc coating appears severely deformed by drawing, with the formation of several
thin short cracks perpendicular to the substrate. Such Such cracks
cracks are are confined to the delta layer, which is
reasonable considering that this phase is more brittle than than thethe others
others [20].
[20].

Figure
Figure 4.
4. SEM
SEM images
images of
of wire
wire cross
cross sections
sections after
after the
the torsion test: (a)
torsion test: (a) Steel
Steel 11 and
and (b)
(b) Steel
Steel 2.
2.

Long vertical cracks are also frequently present in the rest of the coating, at intervals of about
Long vertical cracks are also frequently present in the rest of the coating, at intervals of about
100–150 μm (Figure 5b). These cracks start from the interface with the substrate or from the
100–150 µm (Figure 5b). These cracks start from the interface with the substrate or from the
gamma/delta interface and propagate along both the delta and the zeta layers, stopping when in
gamma/delta interface and propagate along both the delta and the zeta layers, stopping when in
contact with the eta phase that is soft and ductile.
contact with the eta phase that is soft and ductile.
It is interesting to observe that the length of the detached fragment is similar to the distance
It is interesting to observe that the length of the detached fragment is similar to the distance
between two consecutive long cracks. Furthermore, in Figure 5a, one can observe that the left edge of
between two consecutive long cracks. Furthermore, in Figure 5a, one can observe that the left edge
the micro-bulged substrate fits almost perfectly into the cracked coating. These two observations
suggest a possible mechanism for the formation of this kind of defect. It consists of two steps:
(1) pulling the rod through the first drawing dies, a small fragment of the coating in between two
Materials 2017, 10, 264 6 of 12

Materials
Materials 2017,
2017, 10,
10, 264
264 66 of
of 12
12
of the micro-bulged substrate fits almost perfectly into the cracked coating. These two observations
suggest
long a possible
long cracks
cracks is mechanism
is detached,
detached, (2) for the formation
(2) passing
passing in the
in of this kind
the remaining
remaining dies,
dies,of the
defect.
the steelIt substrate
steel consists ofis
substrate istwo steps:in
coined
coined in(1) pulling
the
the “free
“free
the rod
space” through
remaining the first
between drawing
the dies,
substrate a small
and fragment
the die, of
giving the
thecoating
final
space” remaining between the substrate and the die, giving the final appearance to the defect. in between
appearance totwo
the long cracks
defect. is
detached,
Figure (2) passing in the remaining dies, the steel substrate is coined in the
Figure 6a shows that the long vertical cracks are already present in the coating before the rod is
6a shows that the long vertical cracks are already present in the “free
coating space”
before remaining
the rod is
between
drawn. In
drawn. Inthethe
thesubstrate
region and the
region where
where the
the die, givingis
coating
coating isthe final appearance
thinner
thinner and the
and eta to
the eta the defect.
layer
layer is almost
is almost absent,
absent, the the cracks
cracks are
are
able Figure
able to pass6athe
to pass shows
the zinc that
zinc the long
coating
coating vertical On
completely.
completely. cracks
On theare
the alreadywhere
contrary,
contrary, presentthe
where thein coating
the coating
coating is before the
is thicker,
thicker, the rod
the is
extra
extra
drawn.
thickness In the region
consisting where
of the the
ductilecoating
eta is
layerthinner
avoidsand the
the eta layer
propagation is almost
of the
thickness consisting of the ductile eta layer avoids the propagation of the crack to the outer surface absent,
crack tothe
thecracks
outer are able
surface
to pass the
(Figure
(Figure 6b).zinc coating completely. On the contrary, where the coating is thicker, the extra thickness
6b).
consisting
This
This isisofin
inthe ductile eta
agreement
agreement layer
with
with theavoids
the previous
previous the propagation
observation
observation that of thethe
that thecrack to the
defects
defects areouter
are surface
normally
normally (Figure
absent
absent 6b).
where
where
the This
the coating is
coating is in agreement
is thicker.
thicker. Thewith the
The beneficial previous
beneficial rolerole of observation
of the
the ductile that
ductile eta the defects
eta layer
layer would are
would be normally
be to absent
to mitigate
mitigate the where
the coatingthe
coating
coating
failure, is
failure, thicker. The
sustaining
sustaining beneficial
cracked
cracked role of the
fragments
fragments of ductile
of the eta layer
the brittle
brittle zeta,would
zeta, delta be
delta and
and to mitigate
gamma
gamma layersthe coating
layers during
during failure,
the
the
sustaining
forming cracked
process.
forming process. fragments of the brittle zeta, delta and gamma layers during the forming process.

Figure 5. SEM
Figure 5. SEM images
images of
of Steel
Steel 11 wire sections: (a)
wire sections: (a) defect
defect cross
cross section
section and
and (b)
(b) far
far from
from the
the defect
defect and
and
EDS
EDS chemical
chemical analysis
analysis of
of the
the bulged
bulged steel
steel surface.
surface.

Figure
Figure 6.
6. SEM
SEM images
images of
of Steel
Steel 11 rod
rod longitudinal sections.
longitudinal sections.

Numerical
Numerical analysis
analysis was
was applied
applied toto simulate
simulate the
the drawing
drawing ofof aa galvanized
galvanized steel
steel wire
wire containing
containing
Numerical analysis was applied to simulate the drawing of a galvanized steel wire containing
the full
the full detachment
detachment of of the
the coating
coating for
for aa length
length of
of 40
40 μm.
μm. The
The results
results are
are presented
presented inin Figure
Figure 77 that
that
the full detachment of the coating for a length of 40 µm. The results are presented in Figure 7 that
shows the Y-displacements distribution in the area close to the defect. The tendency of steel
shows the Y-displacements distribution in the area close to the defect. The tendency of steel substrate substrate
shows the Y-displacements distribution in the area close to the defect. The tendency of steel substrate
to protrude
to protrude into
into the
the “free
“free space”
space” left
left by
by the
the coating
coating is
is evident,
evident, in
in agreement
agreement with
with the
the morphology
morphology
to protrude into the “free space” left by the coating is evident, in agreement with the morphology
observed in Figure 5a.
observed in Figure 5a.
observed in Figure 5a.
This
This result
result supports
supports thethe hypothesis
hypothesis that
that the
the origin
origin of
of failure
failure is
is the
the detachment
detachment of of aa coating
coating
This result supports the hypothesis that the origin of failure is the detachment of a coating
fragment during
fragment during the
the first
first drawing
drawing steps,
steps, favored
favored byby the
the presence
presence ofof through-thickness
through-thickness cracks
cracks
fragment during the first drawing steps, favored by the presence of through-thickness cracks
(Figure 6b).
(Figure 6b).
(Figure 6b).
Materials 2017, 10, 264 7 of 12
Materials 2017, 10, 264 7 of 12

Figure
Figure 7.
7. FEM
FEMsimulations
simulationsresults:
results: Y-displacements
Y-displacements distribution.
distribution.

The presence of the vertical cracks in the hot dipped Zn coating is not surprising. The coefficient
The presence of the vertical cracks in the hot dipped Zn coating is not surprising. The coefficient
of thermal expansion of the coating layer is higher than that of the substrate steel, accordingly, the
coating layerexpansion
of thermal can sufferof fromthemultiple
coating cracking
layer is higher
during than
cooling,thatdueof the
to thesubstrate
thermally steel, accordingly,
induced tensile
stresses [18,21]. In any case, comparing the galvanizing coatings on the steel rods 1 andinduced
the coating layer can suffer from multiple cracking during cooling, due to the thermally 2, it is
tensile stresses
evident that the[18,21]. In any case,cracks
through-thickness comparing the galvanizing
are present only in thecoatings on the
case of steel steel rods
1 (Figure 8). 1This
andcan2, itbeis
evident that
explained the through-thickness
considering that the two crackscoatings arehave
present only inmicrostructure.
a different the case of steelIn 1 (Figure
the case8). of This
steelcan be
1, the
explained considering that the two coatings have a different microstructure.
columnar grains of the brittle zeta layer are coarser and the thickness of the soft eta layer is smaller In the case of steel 1, the
columnar grains
compared to theofsteelthe brittle
2 (Figurezeta layer are coarser
8a). These and the
conditions thickness
decrease theof toughness
the soft eta of layer
theiscoating,
smaller
compared to
facilitating the the steel 2 (Figure
propagation 8a). These
of cracks under conditions
the action decrease the toughness
of thermally induced of the coating,
tensile stresses.facilitating
the propagation of cracks under the action of thermally induced tensile stresses.
The galvanized coating microstructure is strictly related to the chemical composition of steel. It
is wellTheknown
galvanizedthat coating microstructure
in the process of hot-dipis strictly related toeven
galvanizing, the chemical composition
small amounts of steel.
of silicon in It
the is
well known that in the process of hot-dip galvanizing, even small amounts of
substrate can increase the reactivity of the molten zinc. In steels with a content of Si of about 0.1 wt. %, silicon in the substrate
can obtained
the increase the reactivity
coating exhibits of the
themolten
excessivezinc.growth
In steelsof with a content of Si
the intermetallic of about
layers, 0.1 wt.in%,
resulting the
poor
obtained coating
mechanical exhibits the
and adhesion excessiveThis
properties. growth of the intermetallic
phenomenon is known layers, resulting effect
as the Sandelin in poor mechanical
[22,23]. Also,
and adhesion properties. This phenomenon is known as the Sandelin
P has synergetic activating effects on the reactivity of Si with molten zinc. Their conjoint effect effect [22,23]. Also, P has is
synergetic activating effects on the reactivity of Si with molten zinc. Their
known as equivalent silicon (Sieq) and is defined as: Sieq = %Si + 2.5%P. The recommended equivalent conjoint effect is known as
equivalent
silicon silicon (Sieq )steels
for galvanizing and isisdefined as: Sieqof=0.14%–0.20%
in the range %Si + 2.5%P. or Theless
recommended
than 0.09% [6]. equivalent
Beyondsilicon
these
for galvanizing steels is in the range of 0.14%–0.20% or
limits, the coating has the tendency to be thicker, more porous and brittle. less than 0.09% [6]. Beyond these limits, the
coating
Thehas
Steelthe1tendency to be thicker,
and 2 considered more
in this porous
study haveanda Sibrittle.
eq of 0.25% and 0.21% respectively. These
The Steel 1 and 2 considered in this
values are both above what it is considered the optimal study have a Si eq of 0.25%
rangeandfor
0.21%
the respectively.
galvanizing These values
process. In
are both above what it is considered the optimal range for the galvanizing
particular, the higher value of Sieq of Steel 1 can justify the different coating microstructure and its process. In particular,
the higher
higher valuefor
tendency ofcracking.
Sieq of Steel 1 can justify the different coating microstructure and its higher
tendency for cracking.
The EDS chemical analysis of the coating layers also confirms that the Steel 1 has a higher
The EDS
reactivity withchemical
the molten analysis
zincofrespect
the coating layers
to Steel also confirms
2, showing thatcontents
higher the Steelof 1 has
Fe ainhigher reactivity
both zeta and
with the molten zinc
delta phases (Figure 8). respect to Steel 2, showing higher contents of Fe in both zeta and delta phases
(Figure 8).
Materials 2017, 10, 264 8 of 12
Materials 2017, 10, 264 8 of 12

Figure 8. SEM
SEM images
images of
of longitudinal
longitudinal sections
sections of
of (a)
(a) Steel
Steel 11 and
and (b)
(b) Steel
Steel 2 rods and EDS chemical
analysis of the different coating layers (wt. %).

Starting
Starting from
from these
these considerations,
considerations, the
the high
high carbon
carbon steels
steels processed
processed in
in the
the plant
plant were
were monitored
monitored
to
to put in relation their chemical compositions with the frequency of cracks in galvanized wires.
put in relation their chemical compositions with the frequency of cracks in galvanized wires.
The results, reported in Table 3, show that a direct link exists between the failures and the
The results, reported in Table 3, show that a direct link exists between the failures and the silicon silicon
equivalent
equivalent index.
index. The
The wire
wire made
made with
with aa steel
steel having
having the
the Si
Sieq index above 0.21% displays a high
eq index above 0.21% displays a high
percentage
percentage of
of coating failures, while
coating failures, while steels
steels with
with aa lower
lower Si
Sieq index
index had
had no
no problems.
problems.
eq

Table
Table 3.
3. Relationship
Relationship between
between steel
steel composition
composition and
and wire
wire Zn
Zn coating failure.
coating failure.
Silicon Equivalent Coating Failure
Batch Steel %C %Si %P Silicon Coating Failure
Batch Steel %C %Si %P Index Frequency
Equivalent Index Frequency
1 C82D 0.810 0.215 0.015 0.25 high
1 C82D 0.810 0.215 0.015 0.25 high
2 C82D 0.827 0.188 0.010 0.21 none
2 C82D 0.827 0.188 0.010 0.21 none
33 C76D
C76D 0.7500.750 0.250 0.017
0.250 0.017 0.29 0.29 high
high
44 C72D
C72D 0.7300.730 0.280 0.012
0.280 0.012 0.31 0.31 very high
very high
55 C82D
C82D 0.8350.835 0.183 0.183
0.010 0.010 0.21 0.21 none
none
66 C82D
C82D 0.8330.833 0.190 0.190
0.006 0.006 0.20 0.20 none
none
7 C84D 0.840 0.190 0.009 0.21 none
78 C84D
C82D 0.8400.810 0.190 0.009
0.270 0.016 0.21 0.31 none
very high
89 C82D
C82D 0.8100.840 0.270 0.016
0.240 0.010 0.31 0.27 very high
very high
9 C82D 0.840 0.240 0.010 0.27 very high
All these results confirmed that the formation of the multiple through-thickness cracks, responsible
All these results confirmed that the formation of the multiple through-thickness cracks,
for the failure of the galvanized coating during the torsion test, depends on two main factors:
responsible for the failure of the galvanized coating during the torsion test, depends on two main factors:
1.
1. theintrinsic
the intrinsicbrittleness
brittlenessofofthe
thecoating,
coating,when
whensteel
steelhas
hasthe
theSi
Sieqeqindex
indexabove
above0.21%,
0.21%,
2. thehigh
the highthermal
thermaltensile
tensilestresses
stressesdeveloped
developedduring
duringthe
thecooling
coolingafter
aftergalvanizing.
galvanizing.

Avoiding this problem

Avoiding this problem by by controlling
controlling the
the Si
Sieq
eq index
index always
always below
below the
the limit
limit of
of 0.21%
0.21% isis probably
probably
not
not a viable solution, as silicon is an alloying element essential to improve the mechanical strength
a viable solution, as silicon is an alloying element essential to improve the mechanical strength
and
and the
the homogeneity
homogeneity of of high
high carbon
carbon steels
steels [24]
[24] or
or to
to promote
promote the
the deoxidation
deoxidation of of the
the melt
melt during
during the
the
steelmaking processes [25].
steelmaking processes [25].
AA better
better strategy
strategy could
could bebe trying
trying to
to decrease
decrease thethe thermal
thermal stresses
stresses developed
developed in in the
the coating
coating by
by
reducing
reducing the
the cooling
cooling rate
rate at
at the
the exit
exit from
from the
the galvanizing
galvanizing bath.
bath. To
To test
test this
this approach,
approach, the
the rods
rods made
made
with
with the
the steel
steel from the Batch
from the Batch 99 (see
(see Table
Table 3)
3) were
were galvanized
galvanized in in two
two different
differentways:
ways:
Materials 2017, 10, 264 9 of 12
Materials 2017, 10, 264 9 of 12

- Steel 9A: by using the standard process;

- Steel 9A: by using the standard process;
- Steel 9B: by switching off the air–water spray at the exit from the Zn bath, in order to decrease the
- Steel 9B: by switching off the air–water spray at the exit from the Zn bath, in order to decrease
cooling rate.
the cooling rate.
The longitudinal residual stresses were measured on these samples by means of μXRD2
The longitudinal residual 2
technique. Figure 9 shows the stresses were measured
2D diffraction on these samples
images collected from thebysamples
means of 9AµXRDand 9Btechnique.
and the
Figure 9integrated
relative shows thediffractographs.
2D diffraction images According collected
to thefrom the penetration
limited samples 9Adepth and 9B of andX-raysthe and
relative
the
integrated
small diffractographs.
incidence angle used inAccording to the limited
the experiments, only thepenetration
diffraction depth
peaks of of the
X-rays
outer and the small
layers were
incidence angle
detectable: the used in the experiments,
hexagonal eta phase only the diffraction
(PDF#04-0831) andpeaks
the ofmonoclinic
the outer layers zeta werephase detectable:
FeZn13
the hexagonal eta phase (PDF#04-0831) and the monoclinic
(PDF#65-1238). In both samples, the Debye rings are not continuous but spotty, zeta phase FeZn 13 (PDF#65-1238).
which means In both
that
samples,
the the Debye
crystalline domains ringsareare not continuous
rather large. This isbut spotty,
true whichinmeans
especially the case that of the crystalline
steel sample 9B, domains
where
are air–water
the rather large. sprayThis wasis true especially
switched in themore
off giving case time
of steel sample 9B, to
to crystallites where
solidifythe and
air–water
grow. spray was
switched off giving more time to crystallites to solidify and grow.
The residual stresses were calculated for the eta phase by measuring the deformation of the
(101) The residual
Debye ring.stresses
Positivewere andcalculated
negative for the eta phase
ψ angles by measuring
were considered. Thethed-sin
deformation
2ψ graphs of the (101)
in both
Debye ring. Positive and negative ψ angles were considered. The d-sin 2 ψ graphs in both samples
samples show an elliptical curvature, named ψ-splitting [26], due to shear stresses near the sample
show anprobably
surface, elliptical related
curvature, named ψ-splitting
to interfacial [26], due the
stresses between to shear stresses
eta and zeta near
layers the(Figure
sample10). surface,
It is
probably related to interfacial stresses between the eta and zeta layers
interesting to observe that the air-cooled sample 9B developed normal tensile stresses (+161 MPa) (Figure 10). It is interesting to
observe that the air-cooled sample 9B developed
much higher than those present in the spray-quenched one (+20 MPa). normal tensile stresses (+161 MPa) much higher than
thoseFrom
present in the spray-quenched
a theoretical point of view,one if the(+20 MPa). in thermal shrinkage between zinc and steel is
difference
From a theoretical point of view,
fully accommodated by the elastic deformation of crystal if the difference in thermal
lattice, shrinkage
then the misfit between stresszincin and
the steel
zinc
is fully accommodated by the elastic deformation of crystal lattice,
coating will be more than 700 MPa at room temperature. However, works in literature showed then the misfit stress in the that
zinc
coating
the actual willresidual
be morestresses
than 700measured
MPa at room by XRDtemperature. However,
in the hot-dip zincworks
coatingsin literature
are much showed
lower,that the
in the
actual residual stresses measured by XRD in the hot-dip zinc
order of 100–200 MPa [9]. This is because the major part of the thermal misfit has been coatings are much lower, in the order of
100–200 MPa [9].by
accommodated This is because
plastic the major
deformation of part of thegrains
the zinc thermal misfitbyhas
and/or been accommodated
formation of microcracks by plastic
along
deformation of the
the zinc grain boundaries. zinc grains and/or by formation of microcracks along the zinc grain boundaries.
In the
In the present
present case,case, thethe spray
spray quenched
quenched samplesample shows
shows residual
residual stresses
stresses closeclose toto zero,
zero, probably
probably
because many
because manymicrocracks
microcracks developed
developed in the
in eta
thelayer
eta and
layerrelaxed the tensile
and relaxed thestresses
tensilealmost
stressescompletely.
almost
On the contrary, in the sample 9B, the slower cooling rate gave more time
completely. On the contrary, in the sample 9B, the slower cooling rate gave more time to accommodate to accommodate the misfit
between
the misfitthe coating
between theand the steel
coating andby themeans
steel byof elastic
meansand plasticand
of elastic deformation.
plastic deformation.

Figure
Figure 9. 2D 2Ddiffraction
diffractionimages
imagesand
and integrated
integrated patterns
patterns from
from steel
steel 9A
9A (spray
(spray on)
on) and
and 9B
9B
(spray
(spray off)
off) samples.
Materials 2017, 10, 264 10 of 12
Materials 2017, 10, 264 10 of 12
Materials 2017, 10, 264 10 of 12

2.098  = +20 MPa  = +32 MPa 2.098  = +161 MPa  = +54 MPa
2.098  = +20 MPa  = +32 MPa 2.098  = +161 MPa  = +54 MPa

2.094 2.094
2.094 2.094
(101)

(101)
2.09 2.09
d(101)

d(101)
2.09 2.09
d

d
2.086 2.086
2.086 Spray on 2.086
Spray on Spray off
Spray off
2.082 2.082
2.082 0.00 0.10 0.20 0.30 0.40 2.082 0.00 0.10 0.20 0.30 0.40
0.00 0.10 0.20 0.30 0.40 0.00 0.10 0.20 0.30 0.40
sin2 sin2
sin2 sin2

Figure 10.
Figure 10. d-sin
d-sin222ψ
ψ diagrams of steel
diagramsof
of steel 9A
9A (spray
(spray on)
on) and
and 9B
9B (spray
(spray off)
off) samples.
samples.
Figure 10. d-sin ψ diagrams steel 9A (spray on) and 9B (spray off) samples.

Longitudinal cross sections cut from the samples 9A and 9B confirmed this interpretation,
Longitudinal
Longitudinal crosscrosssections
sectionscutcut from
from the the samples
samples 9A and 9A9Band 9B confirmed
confirmed this interpretation,
this interpretation, showing
showing that the through-thickness cracks are frequently encountered in the spray-quenched
showing that the through-thickness
that the through-thickness cracks are
cracks are frequently frequentlyinencountered
encountered in the spray-quenched
the spray-quenched sample, while in
sample, while in the other one the cracks are always confined just in the delta layer (Figure 11). So, as
sample,
the otherwhile in the
one the other
cracks areone the cracks
always confinedare just
always confined
in the just (Figure
delta layer in the delta
11). layer
So, as(Figure
expected,11).the
So,soft
as
expected, the soft cooling reduced the coating tendency to cracking. It is worth noting that the wire
expected, the softthe
cooling reduced cooling
coatingreduced theto
tendency coating tendency
cracking. to cracking.
It is worth It is the
noting that worth noting
wire that the
produced withwirethe
produced with the steel 9A had a high percentage of failures during the torsion test, while no
produced
steel 9A had with the percentage
a high steel 9A had a high during
of failures percentage of failures
the torsion duringnothe
test, while torsion
failures test,
were while no
observed in
failures were observed in the case of wire produced with the steel 9B.
failures were observed in the case of
the case of wire produced with the steel 9B. wire produced with the steel 9B.
In conclusion, the proper countermeasure to prevent this type of failure was to reduce or
In
In conclusion,
conclusion, the the proper
proper countermeasure
countermeasure to to prevent
prevent thisthis type
type ofof failure
failure was
was toto reduce
reduce or or
completely switch off the air–water sprays when the Sieq index of the rods’ steel exceeds the critical
completely switch off the air–water sprays when the Si index of the rods’ steel
completely switch off the air–water sprays when the Sieq index of the rods’ steel exceeds the critical
eq exceeds the critical
value of 0.21%.
value
value ofof 0.21%.
0.21%.

Figure 11. SEM images of longitudinal sections of (a) steel 9A and (b) steel 9B samples.
Figure 11.
Figure SEM images
11. SEM images of
of longitudinal
longitudinal sections
sections of
of (a)
(a) steel
steel 9A
9A and
and (b)
(b) steel
steel 9B samples.

4. Conclusions
4.
4. Conclusions
Conclusions
This study showed that the cracks of galvanized high carbon steel wires developed during the
This
This study
study showed
showed thatthat the
the cracks of galvanized
galvanized high
high carbon
carbon steel
steel wires developed
developed during
during the the
torsion test are a consequence of preexisting through-thickness cracks in the rods’ coating. During
torsion are aaconsequence
torsion test are consequenceofofpreexisting
preexistingthrough-thickness
through-thickness cracks
cracks in in
thethe rods’
rods’ coating.
coating. During
During the
the drawing process, from these weakened points, small fragments of the coating are detached,
the drawing process, from these weakened points, small fragments of the
drawing process, from these weakened points, small fragments of the coating are detached, creating coating are detached,
creating the final defects.
creating
the final the final defects.
defects.
The presence of multiple through-thickness cracks in the rods’ coating depends mainly on two
The
The presence of
presence of multiple
multiple through-thickness
through-thickness cracks
cracks inin the
the rods’
rods’ coating
coating depends
depends mainly
mainly on on two
two
factors: the high thermal tensile stresses developed during the cooling down at the exit from the
factors:
factors: the
the high
high thermal
thermal tensile
tensile stresses
stresses developed
developed during
during the the cooling
cooling down
down at at the
the exit
exit from
from the the
galvanizing bath and the intrinsic brittleness of the coating when the steel substrate has a Sieq index
galvanizing
galvanizing bathbath and
and the intrinsic brittleness of the coating when the steel substrate has a Sieq eq index
index
above 0.21%. In this case, a coarser and more brittle microstructure is formed and, in particular, the
above
above 0.21%.
0.21%. InIn this
this case,
case, aa coarser
coarser and
and more
more brittle
brittle microstructure
microstructure is is formed
formed and,and, inin particular,
particular, thethe
thickness of the soft eta layer is almost zero, losing its ability to sustain the cracked fragments of
thickness
thickness of of the
the soft
soft eta
eta layer
layer is almost zero, losing its ability to sustain the cracked fragments fragments of of
intermetallics during the forming process.
intermetallics
intermetallics during the forming process.
In order to reduce the thermal stresses developed in the coating and the consequent cracks,
In
In order
order to reduce the thermal thermal stresses
stresses developed
developed in in the
the coating
coating andand the
the consequent
consequent cracks,
cracks,
in-plant tests were performed on steel rods with the Sieq index above 0.21%, by switching off the air–
in-plant
in-plant tests
testswere
wereperformed
performedon onsteel
steelrods with
rods thethe
with SieqSiindex above
index 0.21%,
above by
0.21%, switching
by off
switching the
offair–
the
water spray at the exit from the zinc bath. Measurementseqby micro X-ray diffraction showed that the
water spray at the exit from the zinc bath. Measurements by micro X-ray diffraction
air–water spray at the exit from the zinc bath. Measurements by micro X-ray diffraction showed that showed that the
reduction of cooling rate changed the residual stress state in the coating and the metallographic
reduction of cooling rate changed the residual stress state in the coating and the metallographic
analysis confirmed the absence of through-thickness cracks. This solution completely solved the
analysis confirmed the absence of through-thickness cracks. This solution completely solved the
problem of coating failure in the wire.
problem of coating failure in the wire.
Materials 2017, 10, 264 11 of 12

the reduction of cooling rate changed the residual stress state in the coating and the metallographic
analysis confirmed the absence of through-thickness cracks. This solution completely solved the
problem of coating failure in the wire.
In conclusion, it was proved that an effective countermeasure to prevent this failure consists of
controlling the intensity of the air–water sprays accordingly to the Sieq index of the steel rods.

Acknowledgments: The authors gratefully acknowledge the Chemistry for Technology Laboratory of Brescia
University for the X-ray diffraction equipment availability.
Author Contributions: M. Gelfi and S. Poli conceived, designed and performed the experiments; L. Solazzi
performed the FEM simulations, M. Gelfi and L. Solazzi analyzed the results and wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Elwazri, A.M.; Wanjara, P.; Yue, S. The effect of microstructural characteristics of pearlite on the mechanical
properties of hypereutectoid steel. J. Mater. Sci. Eng. A 2005, 404, 91–98. [CrossRef]
2. Shibli, S.M.A.; Meena, B.N.; Remya, R. A review on recent approaches in the field of hot dip zinc galvanizing
process. Surf. Coat. Technol. 2015, 262, 210–215. [CrossRef]
3. Cresdee, R.B.; Edwards, W.J.; Thomas, P.J.; Voss, G.F. Analysis of beam distortion during hot dip galvanizing.
Mater. Sci. Technol. 1993, 9, 161–162. [CrossRef]
4. Solazzi, L.; Scalmana, R.; Gelfi, M.; la Vecchia, G.M. Effect of Different Corrosion Levels on the Mechanical
Behavior and Failure of Threaded Elements. J. Fail. Anal. Prev. 2012, 12, 541–549. [CrossRef]
5. Gupta, A.K.; Kumar, D.R. Formability of galvanized interstitial-free steel sheets. J. Mater. Process. Technol.
2006, 172, 225–237. [CrossRef]
6. Vagge, S.T.; Raja, V.S.; Narayanan, R.G. Effect of deformation on the electrochemical behavior of hot-dip
galvanized steel sheets. Appl. Surf. Sci. 2007, 253, 8415–8421. [CrossRef]
7. Singh, J.K.; Singh, D.D.N. Studies on defects in galvanized coating on steel wire. Indian J. Chem. Technol.
2012, 19, 361–365.
8. Hu, C.D.; Jiang, S.M.; Li, Y.P.; Yang, F.; Chen, Y.; Yu, G.Q. Effect of inhibition layer and ζ-FeZn_(13) on
adhesion of dual phase steel coating. J. Iron Steel Res. 2013, 25, 37–41.
9. Song, G.M.; Vystavel, T.; van der Pers, N.; de Hosson, J.T.M.; Sloof, W.G. Relation between microstructure
and adhesion of hot dip galvanized zinc coatings on dual phase steel. Acta Mater. 2012, 60, 2973–2981.
[CrossRef]
10. Khondker, R.; Mertens, A.; McDermid, J.R. Effect of annealing atmosphere on the galvanizing behavior of
a dual-phase steel. J. Mater. Sci. Eng. A. 2007, 463, 157–165. [CrossRef]
11. He, S.; van Bael, A.; Li, S.Y.; van Houtte, P.; Mei, F.; Sarban, A. Residual stress determination in cold drawn
steel wire by FEM simulation and X-ray diffraction. Mater. Sci. Eng. A Struct. 2003, 346, 101–107. [CrossRef]
12. Pola, A.; Gelfi, M.; la Vecchia, G.M. Simulation and validation of spray quenching applied to heavy forgings.
J. Mater. Process. Technol. 2013, 213, 2247–2253. [CrossRef]
13. ISO 16120–2:2011. Part 2: Specific requirements for general-purpose wire rod. In Non-Alloy Steel Wire Rod for
Conversion to Wire; International Organization for Standardization: Geneva, Switzerland, 2011.
14. Gelfi, M.; Bontempi, E.; Roberti, R.; Depero, L.E. X-ray diffraction Debye Ring Analysis for stress
measurement (DRAST): A new method to evaluate residual stresses. Acta Mater. 2004, 52, 583–589. [CrossRef]
15. Pola, A.; Gelfi, M.; Depero, L.E.; Roberti, R. Study of annealing temperature effect on stress-corrosion
cracking of aluminum brass heat-exchangers tubes by microdiffraction experiments. Eng. Fail. Anal. 2008,
15, 54–61. [CrossRef]
16. Ajimi, W.T.; Retraint, D.; Montay, G. Structure-mechanical property relationship in Hot-Dip Galvanized
S355k2 + N steel plates. Adv. Mater. Res. 2014, 996, 884–889. [CrossRef]
17. Byon, S.M.; Lee, S.J.; Lee, D.W.; Lee, Y.H.; Lee, Y. Effect of coating material and lubricant on forming force
and surface defects in wire drawing process. Trans. Nonferrous Met. Soc. China 2011, 21, s104–s110. [CrossRef]
18. Iwamoto, S.; Ochiai, S.; Okuda, H. Influence of the Crack Spacing in the Coating Layer on the Progress of
Interfacial Debonding in Galvannealed Steel Pulled in Tension. ISIJ Int. 2009, 49, 431–438. [CrossRef]
Materials 2017, 10, 264 12 of 12

19. ArcelorMittal Europe Long Products—Bars & Rods. Available online: http://barsandrods.arcelormittal.
com/flipflop/Barsandrods/2016_Barsrods_brochure_web/index.html (accessed on 18 December 2016).
20. Okamoto, N.L.; Kashioka, D.; Inomoto, M.; Inui, H.; Takebayashi, H.; Yamaguchid, S. Compression
deformability of Γ and ζ Fe-Zn intermetallics to mitigate detachment of brittle intermetallic coating of
galvannealed steels. Scr. Mater. 2013, 69, 307. [CrossRef]
21. Roy, U.; Ghosh, C. Residual stress analysis in galvannealed coating. Ironmaking Steelmaking 2016, 43, 465–472.
[CrossRef]
22. Marder, A.R. The Metallurgy of Zinc-Coated Steel. Prog. Mater. Sci. 2000, 45, 191. [CrossRef]
23. Sandelin, R.W. Galvanizing characteristic of different types of steel. Wire Wire Prod. 1940, 15, 655–676.
24. Wang, L.; Ma, H.; Li, P.; Wang, X.-J.; Liu, W.-Q. Application of silicon on development of high carbon steel
wire rod. J. Iron Steel Res. 2014, 26, 54–56.
25. Mekhtiyev, A.; Akhmetov, A.; Yudakova, V.; Bulatbayev, F. Experience with ferrosilicoaluminum alloy during
deoxidation of steel. Metalurgija 2016, 55, 47–50.
26. Noyan, I.C.; Cohen, J.B. Residual Stress: Measurement by Diffraction and Interpretation, 1st ed.; Springer:
New York, NY, USA, 1987; pp. 118–119.

© 2017 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/).