metals

Article
The Effect of Microstructural Imperfections on
Corrosion Fatigue of Additively Manufactured
ER70S-6 Alloy Produced by Wire Arc Deposition
Tomer Ron 1 , Galit Katarivas Levy 2, * , Ohad Dolev 1 , Avi Leon 1 , Amnon Shirizly 1 and
Eli Aghion 1
1 Department of Materials Engineering, Ben-Gurion University of the Negev, Beer-Sheva 8410501, Israel;
toron@post.bgu.ac.il (T.R.); dolev.ohad@gmail.com (O.D.); avileon12@gmail.com (A.L.);
a.shirizly@gmail.com (A.S.); egyon@bgu.ac.il (E.A.)
2 Department of Engineering, University of Cambridge, Trumpington Street, CB2 1PZ Cambridge, UK
* Correspondence: gk406@cam.ac.uk




Received: 6 December 2019; Accepted: 30 December 2019; Published: 8 January 2020


Abstract: This study aims at evaluating the effect of microstructure imperfections on the corrosion
fatigue performance of an ER70S-6 alloy produced by wire arc additive manufacturing (WAAM)
process, in a 3.5% NaCl solution. For reference, a regular ST-37 alloy with relatively similar chemical
composition was considered as a counterpart alloy. This was justified by the fact that the ER70S-6
alloy is usually used for conventional welding of ST-37 steel. The results obtained indicated that
while the ST-37 alloy exhibited fatigue strength of 240 MPa in the corrosive solution, the additively
manufactured ER70S-6 alloy showed fatigue strength of only 140 MPa. These differences were related
to microstructural imperfections that are inherently produced during the WAAM process.

Keywords: additive manufacturing; ER70S-6; corrosion; fatigue; steel; wire arc deposition; direct
energy deposition

1. Introduction
Additive manufacturing (AM), processes are principally divided into three main categories:
powder-bed technology (PBT), inkjet printing and blown powder/wire technology. Currently, the most
popular process is PBT, which is practically implemented by means of selective laser melting (SLM)
and electron beam melting (EBM) [1–5]. The wire arc additive manufacturing (WAAM) process is
carried out using an electric arc as the energy source and consumable wires as the filler material for
layer-by-layer metal deposition controlled by 3D CAD software, under an inert gas atmosphere [6,7].
Compared to powder-bed technologies, the WAAM process is significantly more attractive and
cost-effective. This is manifested in terms of energy consumption (90% less than PBT), production cost,
including raw materials, (80% less than PBT) and component dimensions that are not limited to the
printing cell size [8–15]. In addition, the deposition rate of the raw material in the WAAM process is
about 160 g/min [16], which is significantly higher than the 10 g/min obtained by conventional PBT
processes [17]. The main disadvantage of WAAM technology compared to PBT relates to its inherent
limitation in terms of possible geometrical structures that can be produced. Practically, the WAAM
process can be used to produce bulk or hollow geometries that enable the deposition-tool-free access to
the deposition area [18].
Currently, most of the research related to WAAM processes has focused on optimizing the printing
parameters, including tool path planning, as well as on analyzing the consequent thermal and residual
stresses that are developed during the production process [19]. Relatively limited attention has been

Metals 2020, 10, 98; doi:10.3390/met10010098 www.mdpi.com/journal/metals

Metals 2020, 10, 98 2 of 10

devoted to microstructural imperfections generated during the WAAM process and their subsequent
effect on material properties. These imperfections mainly include impurities and solidification defects
such as porosity, lack of fusion and hot cracks [20] that can lead to premature fatigue failure [21]
as well as to deterioration in the corrosion resistance. The present study aims to evaluate the effect
of microstructure imperfections on corrosion fatigue behavior of an ER70S-6 alloy produced by the
WAAM process. It should be pointed out that the ER70S-6 alloy is usually used for conventional
welding of ST-37 steels [22] that have very similar chemical compositions and mechanical properties.
Hence, the present study considers ST-37 steel as a counterpart alloy for reference [23].

2. Materials and Methods

The chemical composition (in wt.%) of the ER70S-6 alloy used for the WAAM process was:
Fe, 0.072% C, 1.248% Mn, 0.761% Si, 0.015% P, 0.0053% S, 0.008% Ni, 0.014% Cr, 0.002% Mo, while the
composition of its counterpart ST-37 alloy was: Fe, 0.15% C, 0.491% Mn, 0.073% Si, 0.008% P, 0.009% S,
0.03% Ni, 0.001% Cr, 0.008% Mo. The tested samples were machined from hollow cylindrical
components produced by the WAAM process using 1.2 mm wire of ER70S-6. The dimensions of the
cylindrical components were: height 120 mm, mid-wall radius 55 mm and wall thickness 15 mm [24].
The deposition process was carried out by a Cloos Rotrol V7.13 (CLOOS, Haiger, Germany) robot
using Quinto 503 SD welding system with a programmed pathway controlled by a CAD model.
The deposition process parameters included: slicing layer thickness 2 mm, tangential deposition speed
14 cm/min, electrical current 210 A, voltage 23.9–24.1 V, pulse frequency 120 Hz with duration of 2.5 ms,
independently determined wire feed-rate 6.1 m/min and protective gas atmosphere with composition
98% argon and 2% oxygen.
Microstructure examination of metallographic specimens and fracture surfaces was carried out
using optical and scanning electron microscopy (SEM; JEOL-5600; JEOL Ltd. Tokyo, Japan) [25].
Metallographic specimens were prepared by polishing up to 0.04 µm roughness, following etching
with Nital solution (HNO3 (70%) 5 mL, ethanol 95 mL) for 10 s. The electrochemical examinations
included open circuit potential, potentiodynamic polarization analysis and electrochemical impedance
spectroscopy (EIS) assessment using a Bio-Logic SP-200 potentiostat equipped with Ec-Lab software
v11.18 (BioLogic Science Instruments, Seyssinet-Pariset, France). The polarization analysis was
performed with a standard three-electrode cell using a saturated calomel electrode (SCE) as a reference
electrode [26]. The scanning rate of the potentiodynamic polarization analysis was 0.5 mV/s. The EIS
measurements were carried out between 10 kHz and 0.015 Hz at a 10 mV amplitude signal after
360 min of getting open circuit potential. Prior to the electrochemical testing, the samples were cleaned
in an ultrasonic bath for 5 min, washed with alcohol, and dried in hot air.
The corrosion fatigue performance was examined under high cycle fatigue conditions in a 3.5%
NaCl solution and in air (for reference) using a rotting-beam fatigue machine (Satec R.R.Moore;
INSTRON, Norwood, MA, USA) at a frequency of 50 Hz. The dimensions of the cylindrical fatigue
specimens were: total length 80 mm and diameter at the gauge area 6 mm. The surface of all the
fatigue specimens was polished up to 2500 grit. In order to obtain an S–N curve, the fatigue strength
was examined by measuring the maximum applied stress versus the number of cycles to failure.

3. Results
The microstructure of the ER70S-6 alloy in the XZ plane, as produced by the WAAM process,
is shown in Figure 1. This reveals a typical microstructure of low carbon steel with a ferrite matrix and a
relatively reduced amount of a secondary pearlite phase, as expected from the limited amount of carbon
(0.072% C) and the rapid solidification conditions of the WAAM process [23]. In addition, clear inherent
microstructural imperfections were present, as can be discerned in terms of porosity (0.15% by image
analysis), impurities (0.08% by image analysis) and lack of fusion (0.04% by image analysis). All those
defects can have a significantly detrimental effect on the mechanochemical behavior of the alloy, especially
under cyclic loading conditions. The microstructure of the counterpart ST-37 alloy is shown in Figure 2,
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pearlite phase due to the higher content of carbon (0.15% C) present in this alloy.

Figure 1. Typical microstructures of additively manufactured ER70S-6 alloy in the XZ plane: (a)
Figure
optical Typical
1. microstructures
1. microscopy;
Figure Typical microstructuresof additively
(b–d) scanning of manufactured
additively
electron ER70S-6
manufactured
microscopy. alloy
ER70S-6 in the
alloy in XZ
the plane: (a) optical
XZ plane: (a)
microscopy; (b–d) scanning electron microscopy.
optical microscopy; (b–d) scanning electron microscopy.

Figure 2. Typical microstructure of the counterpart ST-37 alloy: (a) optical microscopy; (b) scanning
Figure 2. Typical microstructure of the counterpart ST-37 alloy: (a) optical microscopy; (b) scanning
electron
Figure microscopy.
2.microscopy.
electron Typical microstructure of the counterpart ST-37 alloy: (a) optical microscopy; (b) scanning
electron microscopy.
The mechanical properties of an additively manufactured ER70S-6 alloy and its counterpart ST-37
The mechanical properties of an additively manufactured ER70S-6 alloy and its counterpart ST-
alloy were
Thewere
37 alloy measured
mechanical
measuredin terms
properties
in termsof
ofoftensile
antensile strength
additively (475.7±± 2.3
(475.7
manufactured
strength and 611.2
2.3ER70S-6
and 611.2 ±±12.9
alloy 12.9MPa,
and itsMPa, respectively),
counterpart ST-
respectively),
elongation
37 (34.6%
alloy were
elongation ± 3.6%
measured
(34.6% and
± 3.6%inand 12.6%
terms
12.6% ± 0.2%,
of tensile respectively)
± 0.2%,strength (475.7and
respectively) and
± 2.3 hardness
and 611.2
hardness (192.4
± 12.9
(192.4 ± 6
± 6MPa, and
and 259.1 ± 15± HV,
259.1 15 HV,
respectively),
respectively)
elongation
respectively) [23].
[23].The
(34.6% The relatively
± 3.6% and 12.6%
relatively lower
lower mechanical
± 0.2%, strength
respectively)
mechanical strength and and increased
hardness
and (192.4
increased ductility
± 6 and
ductility of
thethe
of 259.1 ±additively
15 HV,
additively
manufactured
respectively) ER70S-6
[23]. The alloy are
relatively mainly
lower related
mechanical to the increased
strength and content
increased
manufactured ER70S-6 alloy are mainly related to the increased content of carbon and subsequently of carbon
ductility and
of the subsequently
additively
increased
increased amount
manufactured amount ofofpearlite
ER70S-6 alloyphase
pearlite are in
mainly
phase in the counterpart
therelated ST-37alloy.
to the increased
counterpart ST-37 alloy.
content of carbon and subsequently
The
increased
The outcomes
amount of
outcomes ofelectrochemical
of pearlite phase inexamination
electrochemical the counterpart
examination ofthe
of the additively
ST-37 manufactured
alloy. manufactured
additively ER70S-6
ER70S-6 alloy
alloy andand
The outcomes
counterpart
counterpart ST-37
ST-37 of electrochemical
alloy
alloyininterms
termsofofopenopenexamination
circuit of the additively
circuitpotential
potential versus manufactured
saturated
versus saturated calomelER70S-6
calomel electrode
electrode alloy and
(SCE)
(SCE) inin a
counterpart
a 3.5% NaCl ST-37 alloy
solution in
are terms
shown ofin open
Figurecircuit
3. potential
This shows versus
that saturated
the calomel
electrochemical
3.5% NaCl solution are shown in Figure 3. This shows that the electrochemical tendencies of the two electrode
tendencies (SCE)
of in
the
atwo
3.5%
alloys wereNaCl
alloys solution
were
quite quite
similar,are shown although
similar,
although in
theFigure 3.
theThis
stabilization shows that(passivation
stabilization
(passivation the electrochemical
phase) phase)
of the tendencies
of
additively of the
themanufactured
additively
two
ER70S-6 alloys
alloywere
manufactured was quitealloy
ER70S-6
obtained similar,
atwas although
obtained
a slightly atthe
higher stabilization
a slightly
potential.higher (passivation
potential.
This This phase)
result complies result of the
complies
with additively
with the
the results of the
manufactured
results of the ER70S-6
immersion alloy
test was
and obtained
salt spray at a slightly
testing in higher
the same potential.
corrosive
immersion test and salt spray testing in the same corrosive environment as obtained by a previous This result
environment complies
as with
obtained the
by
results
a of
previous the immersion
study of
study of the authors [23]. the test
authorsand salt
[23]. spray testing in the same corrosive environment as obtained by
a previous study of the authors [23].
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Figure 3.
Figure 3. Open
Open circuit
circuit potential
potentialof
ofadditively
additivelymanufactured
manufacturedER70S-6
ER70S-6alloy
alloyand
andcounterpart
counterpartST-37 alloy
Figure 3. Open circuit potential of additively manufactured ER70S-6 alloy and counterpart
ST-37
in 3.5%alloy
NaClinsolution.
3.5% NaCl solution.
ST-37 alloy in 3.5% NaCl solution.
The cyclic
The cyclic potentiodynamic
potentiodynamic polarization
polarization analysis
analysis results
results for
for additively
additively manufactured
manufactured ER70S-6ER70S-6
The cyclic potentiodynamic polarization analysis results for additively manufactured ER70S-6
alloy and its counterpart ST-37 alloy are shown in Figure 4. This reveals that the
alloy and its counterpart ST-37 alloy are shown in Figure 4. This reveals that the cyclic polarizationcyclic polarization
alloy and its counterpart ST-37 alloy are shown in Figure 4. This reveals that the cyclic polarization
curves of
curves of the
the two
two alloys
alloys were
were basically
basically similar,
similar, without
without any
any tendency
tendency of of one
one of
of the
the alloys
alloys toto shift
shift its
its
curves of the two alloys were basically similar, without any tendency of one of the alloys to shift its
polarization curve
polarization curve toto higher
higher current
current densities
densities that
that could
could reflect
reflect significant
significant differences
differences in in corrosion
corrosion
polarization curve to higher current densities that could reflect significant differences in corrosion
resistance[27,28].
resistance [27,28].InInaddition,
addition,thethemode
mode ofof
thethe cyclic
cyclic hysteresis
hysteresis of the
of the twotwo alloys
alloys afterafter passing
passing the Eswthe
resistance [27,28]. In addition, the mode of the cyclic hysteresis of the two alloys after passing the
Esw (switch)
(switch) potential
potential and reaching
and reaching the Eprot
the Eprot (protection)
(protection) potential
potential was wasveryvery similar.
similar. In both
In both cases,
cases, the
Esw (switch) potential and reaching the Eprot (protection) potential was very similar. In both cases,
the cyclic
cyclic hysteresis
hysteresis mode represents
mode represents a general/uniform
a general/uniform corrosion
corrosion attack. attack. Tafel measurements
Tafel extrapolation extrapolation
the cyclic hysteresis mode represents a general/uniform corrosion attack. Tafel extrapolation
measurements
disclosed disclosed
that the corrosion that theofcorrosion
rate rate of
the additively the additively
manufactured manufactured
alloy alloy was
was quite similar quite
to that of
measurements disclosed that the corrosion rate of the additively manufactured alloy was quite
similar
the to that of
counterpart the (0.087
alloy counterpart alloy
and 0.134 (0.087respectively),
mmpy, and 0.134 mmpy,
whichrespectively), which in both
in both cases represents cases
adequate
similar to that of the counterpart alloy (0.087 and 0.134 mmpy, respectively), which in both cases
representsresistance.
corrosion adequate corrosion
Altogether,resistance.
the resultsAltogether, the results of the
of the potentiodynamic potentiodynamic
polarization polarization
analysis agreed with
represents adequate corrosion resistance. Altogether, the results of the potentiodynamic polarization
analysis
the agreed
results withby
obtained the
theresults
open obtained by the open
circuit potential circuit potential assessment.
assessment.
analysis agreed with the results obtained by the open circuit potential assessment.

AM
AMER70S-6
ER70S-6 ST-37
ST-37
Ecorr (V) −0.65 ± 0.002
−0.65 ± 0.002 −0.56 ± 0.03
Ecorr (V)
Ecorr (V) −0.65 ± 0.002 −0.56 ± 0.03
−0.56 ± 0.03
Icorr (μA)
Icorr (µA) 6.12±±0.6
6.12 0.6 6.6 ±
6.60.7± 0.7
Icorrrate
Corrosion (μA) (mmpy) 6.12
0.13 ± ±0.01
0.6 6.60.01
0.08 ± ± 0.7
Corrosion rate (mmpy) 0.13 ± 0.01 0.08 ± 0.01
Corrosion rate
Figure 4. Cyclic potentiodynamic (mmpy) analysis
polarization 0.13
of ±additively
0.01 0.08 ± 0.01ER70S-6 alloy and
manufactured
Figure 4. ST-37
reference Cyclicalloys
potentiodynamic polarization
in 3.5% NaCl solution. analysis of additively manufactured ER70S-6 alloy and
Figure 4. Cyclic potentiodynamic polarization analysis of additively manufactured ER70S-6 alloy and
reference ST-37 alloys in 3.5% NaCl solution.
reference ST-37 alloys in 3.5% NaCl solution.
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The results of the EIS analysis relating to the additively manufactured ER70S-6 and reference
ST-37The
The results
alloys in of
results ofthe
terms EIS
theofEIS analysis
analysis
Nyquist relating
relating
plots totothe
and Bode the additively
additively
plots manufactured
are shown manufactured ER70S-6
in Figure 5a,b.ER70S-6 and
andreference
The Nyquist reference
plots of
ST-37
both alloys were quite similar, with a small increase in the radius of the counterpart alloy plots
ST-37 alloys
alloys in
in terms
terms of
ofNyquist
Nyquist plots
plots and
and Bode
Bode plots
plots are
are shown
shown ininFigure
Figure 5a,b.
5a,b.The
The Nyquist
Nyquist plots
that ofof
may
both
both alloys
alloysawere
illustrate veryquite
were quitesimilar,
minor similar, with
withaasmall
improvement in theincrease
small increase
corrosionininresistance.
the
theradius
radiusof ofthe
The the counterpart
counterpart
Bode magnitude alloy
alloy that
thatmay
diagram may
that
illustrate
illustrate a avery
very minor
minor improvement
improvement in
inthe
the corrosion
corrosion resistance.
resistance. The
The Bode
Bode magnitude
magnitude
introduces the solution resistance (R1) and the total resistance of the system (Rtotal) clearly indicates diagram
diagram that
that
introduces
introduces the
thesolution
that the corrosion solution resistance
resistance
resistances (R1)
of the(R1) and
andthe
additively total
total resistance
themanufactured
resistance of
of the
ER70S-6the system
system (R
(Rtotal
alloy and total) )clearly
clearly
reference indicates
indicates
ST-37 alloys
that
that
werethe
the corrosion
corrosion
similar. The resistances
resistances ofofthe
theadditively
related electrical additively
equivalent manufactured
manufactured
circuit, as wellER70S-6
as thealloy
ER70S-6 alloyand
fitted andreference
referenceST-37
parameters, ST-37
are alloys
alloys
shown in
were
were
Figuresimilar.
similar.
6. The The
The related
related
fitted electrical
electrical
parameters equivalent
equivalent
were: circuit,
circuit,
R1, solution asaswell
wellasas
resistance; the
R2 the fitted
and C1 parameters,
fitted parameters,
represent are
theareshown
shown
double inin
layer
Figure
Figure
[29]; R36.6. The
The fitted
and fitted
C2 parameters
parameters
represent were: R1,
were:
the charge R1,solution
solution
transfer resistance;
andR2
resistance;
resistance R2 andand
capacitor C1C1 represent
represent
[30]. thethe double
double layerlayer
[29];
[29];
R3 andR3 and C2 represent
C2 represent the charge
the charge transfer
transfer resistance
resistance and and capacitor
capacitor [30]. [30].

Figure 5. Electrochemical impedance spectroscopy of additively manufactured ER70S-6 alloy and

Electrochemicalimpedance
Figure5.5.Electrochemical
Figure impedancespectroscopy
spectroscopyofofadditively
additivelymanufactured
manufacturedER70S-6
ER70S-6alloy
alloyand
and
reference ST-37 alloys in 3.5% NaCl solution: (a) Nyquist diagram; (b) Bode magnitude diagram.
referenceST-37
reference ST-37alloys
alloysin
in3.5%
3.5%NaCl
NaClsolution:
solution:(a)
(a)Nyquist
Nyquistdiagram;
diagram;(b)
(b)Bode
Bodemagnitude
magnitudediagram.
diagram.

R1[Ohm]
R1 [Ohm] C1C1 [F][F] R2R2 [Ohm] C2C2
[Ohm] [F][F] R3R3 [Ohm]
[Ohm]
AM ER70S-6 18.32 −4 -4
6.31 2.44∙10
−4 -4
-4 31.98
AM
AM ER70S-6 18.32
ER70S-6 18.32 2.55·10
2.55∙10 6.31
6.31 2.44·10
2.44∙10 31.98
31.98
ST-37
ST-37 18.65 4.13·10
18.65 4.13∙10
−4 -4 18.86 1.14·10
1.14∙10
−3 -3 42.15
ST-37 18.65 2.55∙10-4-4 18.86
4.13∙10 18.86 1.14∙10-3
42.15
42.15
Figure6.6.Electrical
Figure Electricalequivalent
equivalent circuit
circuitand
andrelated
relatedfitted
fittedparameters
parametersfor
forNyquist
Nyquistand
andBode
Bodediagrams
diagrams
Figure 6. Electrical
plotsshown equivalent
shownininFigure
Figure5.5. circuit and related fitted parameters for Nyquist and Bode diagrams
plots
plots shown in Figure 5.
The
Thehigh
highcycle
cyclefatigue
fatiguestrengths
strengthsof
ofadditively
additivelymanufactured
manufacturedER70S-6
ER70S-6alloy
alloyandandits
itscounterpart
counterpart
ST-37The
ST-37 highinin
alloy,
alloy, cycle
air fatigue
airand
and strengths
inin3.5%
3.5% NaCl of additively
NaClsolution,
solution, in manufactured
interms
terms of
oftheir
theirS–N ER70S-6
S–N curves,alloy
curves, are and itsin
are shown
shown incounterpart
Figure
Figure 7a,b.
7a,b.
ST-37 alloy,
Although
Althoughthe in air and
theshapes
shapesof in 3.5%
ofthe
thetwoNaCl
twoS–Nsolution,
S–Ncurves in
curves of terms
ofboth of their
bothalloys
alloys in S–N
inthe curves,
theair
airwere are
werequiteshown in
quitesimilar, Figure
similar,the 7a,b.
thefatigue
fatigue
Although
strength the
strength of shapes of
of ER70S-6 the(220
alloy
alloy two MPa)
(220 S–N
MPa)curves of both reduced
wasrelatively
was relativelyalloys in compared
reduced the air were
compared quite
to
to that ofsimilar,
that of the
the ST-37 the fatigue
ST-37
alloyalloy
(230
strength of ER70S-6 alloy (220 MPa) was relatively reduced compared to that of the
MPa). This can mainly be attributed to the differences in carbon content, the amount of secondary ST-37 alloy (230
MPa). This can mainly be attributed to the differences in carbon content, the amount of secondary
Metals 2020, 10, 98 6 of 10

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(230 MPa).2019,This
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canPEER REVIEW
mainly 6 of 10
be attributed to the differences in carbon content, the amount of secondary
phase and the subsequent mechanical properties of the two alloys. This explanation agrees with the
phase and the subsequent mechanical properties of the two alloys. This explanation agrees with the
results obtained by Tayanc et al. [31], who found that the fatigue strength of carbon steels increases
results obtained by Tayanc et al. [31], who found that the fatigue strength of carbon steels increases
as the carbon content is higher. In addition, it should be pointed out that both alloys had a clear
as the carbon content is higher. In addition, it should be pointed out that both alloys had a clear
endurance limit, which means that below a certain stress level, the two alloys will never fail due to
endurance limit, which means that below a certain stress level, the two alloys will never fail due to
cyclic loading alone [32]. In parallel, while the fatigue behavior of the counterpart ST-37 alloy was
cyclic loading alone [32]. In parallel, while the fatigue behavior of the counterpart ST-37 alloy was
nearly unchanged by the transition from air to a corrosive environment, a dramatic modification was
nearly unchanged by the transition from air to a corrosive environment, a dramatic modification was
experienced
experiencedbybythe theadditively
additivelymanufactured ER70S-6 alloy.
manufactured ER70S-6 alloy. InInthis
thiscase,
case,the
thefatigue
fatigue strength
strength of of
thethe
additively manufactured alloy was reduced from 230 MPa in air to 140 MPa in the corrosive
additively manufactured alloy was reduced from 230 MPa in air to 140 MPa in the corrosive solution, solution,
and nono
and endurance
endurancelimit limitcould
couldbe
beclearly
clearlyidentified.
identified.

Figure 7. S–N curve obtained in air and in 3.5% NaCl solution for (a) additively manufactured ER70S-6
Figure 7. S–N curve obtained in air and in 3.5% NaCl solution for (a) additively manufactured ER70S-
alloy and (b) counterpart ST-37 alloy.
6 alloy and (b) counterpart ST-37 alloy.

The fracture surface of ST-37 alloys after high cycle fatigue failure in an air atmosphere at a stress
The fracture surface of ST-37 alloys after high cycle fatigue failure in an air atmosphere at a stress
of 240 MPa is shown in Figure 8. The initial crack was produced at the external surface and slowly
of 240 MPa is shown in Figure 8. The initial crack was produced at the external surface and slowly
propagated
propagated across
acrossthethematerial
materialbulkbulkin inaadirection
direction perpendicular
perpendicular to tothe
theloading
loadingaxis.axis.AsAs a result,
a result, thethe
cross-sectional
cross-sectional area was reduced to a point where it could not carry the load and the material failed in
area was reduced to a point where it could not carry the load and the material failed
tension [32].[32].
in tension Consequently,
Consequently, thethefracture
fracturesurface
surfaceofofbothbothalloys
alloys was basicallydivided
was basically dividedinto intotwotwo main
main
regions:
regions: the smooth regions where the crack propagation took place and the rough region where thethe
the smooth regions where the crack propagation took place and the rough region where
final overload
final overload cracking
crackingoccurred.
occurred.However,
However,the therough
rough region
region of thethe additively
additivelymanufactured
manufacturedER70S- ER70S-6
alloy (Figure
6 alloy (Figure9a)9a)was relatively
was relatively enlarged
enlargedcompared
comparedto to that
that of the
the counterpart
counterpartST-37 ST-37alloy.
alloy. This
This could
could
explain
explain thetheincreased
increasednumber
numberofofcycles cycles toto failure
failure (3,554,000
(3,554,000 vs.vs. 1,380,000
1,380,000cycles)
cycles)generated
generated bybythethe
relatively
relatively increasedstrength
increased strengthofofST-37
ST-37alloy.
alloy.
While
While thethe fracturesurface
fracture surfacecharacteristics
characteristics of the ST-37 ST-37alloy
alloyafter
afterhigh
highcycle
cyclefatigue
fatiguefailure in 3.5%
failure in 3.5%
NaCl
NaCl solutionwere
solution werequite
quitesimilar
similarto to the
the results
results obtained
obtainedin inair,
air,the
thefracture
fracturesurface
surface ofof
thetheadditively
additively
manufactured
manufactured ER70S-6alloy
ER70S-6 alloyininthe
thecorrosive
corrosive environment
environment was wassignificantly
significantlydifferent
different from
from thethe
results
results
in air, as shown in Figure 9a,b. According to Figure 9b the fracture surface
in air, as shown in Figure 9a,b. According to Figure 9b the fracture surface included three main included three main areas:
areas:
(i) a small smooth area with a crack initiation close to the south pole; (ii)
(i) a small smooth area with a crack initiation close to the south pole; (ii) a large smooth area at the a large smooth area at the
center
center with
with anan elongated
elongated crack
crack initiation;
initiation; andand (iii)
(iii) a rough
a rough area
area at at
thethe north
north polepole that
that represents
represents thethe
final
final overload failure. The two smooth areas represent sections where natural crack propagation took
overload failure. The two smooth areas represent sections where natural crack propagation took place.
place. However, it was evident that the cracking phenomena at the south pole included more than
However, it was evident that the cracking phenomena at the south pole included more than one crack
one crack initiation. It is believed that under the corrosive solution the inherent microstructural
initiation. It is believed that under the corrosive solution the inherent microstructural imperfections in
imperfections in the form of lack of fusion, impurities and porosity created favorable conditions for
the form of lack of fusion, impurities and porosity created favorable conditions for a localized corrosion
a localized corrosion attack. Consequently, those corrosive sites acted as an incubation phase for crack
attack. Consequently, those corrosive sites acted as an incubation phase for crack initiation and fatigue
Metals 2019,
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2020, 9, FOR PEER REVIEW 77of
of 10
10
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initiation and fatigue failure. Figure 9c shows a close-up view of the fracture surface that highlights
failure. Figure
initiation 9c shows
and fatigue a close-up
failure. Figureview of theafracture
9c shows close-upsurface
view ofthat
thehighlights the clear
fracture surface thatpresence of
highlights
the clear presence of porosity generated during the printing process.
porosity generated during the printing process.
the clear presence of porosity generated during the printing process.

Figure 8. Fractography analysis of ST-37 alloy after high cycle fatigue failure in air, with 240 MPa load
Fractography analysis of ST-37 alloy after high cycle fatigue failure in air, with 240 MPa load
Figure 8. Fractography
and 3,554,000 cycles.
and
and 3,554,000
3,554,000 cycles.
cycles.

Fractography analysis
Figure 9. Fractography analysis of
of additively
additively manufactured
manufactured ER70S-6
ER70S-6 alloy
alloy after
after high
high cycle
cycle fatigue
Figure 9. Fractography analysis of additively manufactured ER70S-6 alloy after high cycle fatigue
failure
failure (a) in air, with 230 MPa load and 1,380,000 cycles; (b,c) in 3.5% NaCl solution, with 220 MPa
failure (a) in air, with 230 MPa load and 1,380,000 cycles; (b,c) in 3.5% NaCl solution, with 220 MPa
load and 11,987,000 cycles.
load and 11,987,000 cycles.
4. Discussion
4. Discussion
4. Discussion
Although the corrosion resistance of the additively manufactured ER70S-6 alloy and its counterpart
Although the corrosion resistance of the additively manufactured ER70S-6 alloy and its
ST-37Although
alloy wasthe quitecorrosion
similar inresistance of the
terms of their open additively manufactured
circuit potential, ER70S-6 alloy
potentiodynamic and its
polarization,
counterpart ST-37 alloy was quite similar in terms of their open circuit potential, potentiodynamic
counterpart
and ST-37 alloy
electrochemical was quite
impedance similar in analysis,
spectroscopy terms of their fatigue
open circuit
behaviorpotential,
in a 3.5%potentiodynamic
NaCl solution
polarization, and electrochemical impedance spectroscopy analysis, their fatigue behavior in a 3.5%
polarization,
was and different.
significantly electrochemical
This was impedance
obtained spectroscopy
in spite of theanalysis,
fact that their
their fatigue
fatigue behavior in a in
3.5%
NaCl solution was significantly different. This was obtained in spite of the factperformance
that their fatigue an
NaCl
air solution was relatively
atmosphere significantly different.
similar, This awas
apart from obtained
minor in spite
difference created of by
theanfact that their
increased fatigue
amount of
performance in an air atmosphere was relatively similar, apart from a minor difference created by an
performance in an air
carbon in the ST-37 alloy. atmosphere was relatively similar, apart from a minor difference created by an
increased amount of carbon in the ST-37 alloy.
increased amount
The main
main of carbon
difference in thethe
between ST-37
twoalloy.
alloys in
in terms
terms ofof fatigue
fatigue behavior
behavior in in the
the corrosive
corrosive solution
solution
The difference between the two alloys
was The main
related to difference
the fact thatbetween
the the two
fatigue alloys
strength ofin
theterms of fatigue
additively behavior inalloy
manufactured the corrosive
was solution
significantly
was related to the fact that the fatigue strength of the additively manufactured alloy was significantly
was related
reduced to the fact thatofthe
compared thefatigue strength of the additively manufactured alloy was significantly
reduced comparedtotothat that of counterpart
the counterpartST-37 alloy.
ST-37 WhileWhile
alloy. the ST-37
the alloy
ST-37showed fatigue
alloy showed strength
fatigue
reduced
of 230 MPa compared
and a to endurance
clear that of thelimit
counterpart
in the ST-37 alloy.
corrosive While
solution, the the ST-37 manufactured
additively alloy showedER70S-6fatigue
strength of 230 MPa and a clear endurance limit in the corrosive solution, the additively
strength
alloy showedof 230
no MPa and limit
endurance a clear
and endurance
continued limit
to fail in to
up the corrosive
fatigue solution,
strength of 140 the additively
MPa (Figure 7).
manufactured ER70S-6 alloy showed no endurance limit and continued to fail up to fatigue strength
manufactured
The fact that ER70S-6
the definite alloy showedlimitno endurance limit andmanufactured
continued to fail upobtained
to fatigue instrength
of 140 MPa (Figure 7). Theendurance of the
fact that the definite additively
endurance limit of the additivelyalloy manufactured airalloy
was
of 140 MPa (Figure 7). The fact that the definite endurance limit of the additively manufactured alloy
obtained in air was lost due to its exposure to a corrosive environment is known as corrosion fatigue
obtained in air was lost due to its exposure to a corrosive environment is known as corrosion fatigue
Metals 2020, 10, 98 8 of 10

lost due to its exposure to a corrosive environment is known as corrosion fatigue [32]. According
to this phenomenon, the simultaneous action of fatigue loading and a corrosive environment can
produce a localized corrosion attack such as pitting that subsequently generates stress corrosion
sites that promote fatigue cracking. Following this insight, it is believed that the reason for the
significant reduction in fatigue strength as well as the lack of a definite endurance limit of the additively
manufactured alloy can be attributed to the inherent microstructural imperfections found in this
material. These imperfections, in the form of porosity, impurities and lack of fusion, can act as corrosive
sites that stimulate fatigue cracking. This assumption was also strongly supported by the results
of the fracture surface analysis (Figure 9b) that showed multiple crack initiations from the external
surface. The assumption that surface defects in steels can generate fatigue cracking that reduces the
fatigue strength and, consequently, eliminates the definite endurance limit is already well known and
understood [33–35].
In summary, the obtained results clearly demonstrate that the fatigue failure of an additively
manufactured ER70S-6 alloy in air was purely mechanical, while in a 3.5% NaCl solution this failure
was significantly affected by the corrosive environment which created the necessary conditions for
corrosion fatigue. The corrosion fatigue failure was mainly attributed to the presence of microstructural
imperfections produced during the WAAM process. The fact that the counterpart ST-37 alloy did
not experience a reduction in the fatigue strength in the corrosive solution compared to its fatigue
strength in air can be related to the absence of typical microstructural imperfections present in the
additively manufactured ER70S-6 alloy. This was mainly related to imperfections such as lack of
fusion and porosity that reasonably stimulate localized corrosion attack and consequent premature
fatigue cracking.

5. Conclusions
In spite of the fact that the general corrosion performances, as well as the fatigue behaviors in air,
of additively manufactured ER70S-6 and its counterpart ST-37 alloys, were quite similar, their fatigue
behaviors in 3.5% NaCl solution were dramatically different. The fatigue strength of ST-37 alloy in the
corrosive solution was maintained at 240 MPa with a definite endurance limit, while the additively
manufactured ER70S-6 alloy showed fatigue strength of only 140 MPa. This was explained in terms
the inherent microstructural imperfections present in the additively manufactured alloy in the form
of porosity, impurities and lack of fusion that promote localized corrosion attacks and consequently
stimulate fatigue cracking.

Author Contributions: E.A., A.S. and T.R. conceived, designed and performed the experiments; G.K.L., A.L.
and O.D. assisted in analyzing the data; E.A. and T.R. wrote the paper. All authors have read and agreed to the
published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Rodrigues, T.A.; Duarte, V.; Avila, J.A.; Santos, T.G.; Miranda, R.M.; Oliveira, J.P. Wire and arc additive
manufacturing of HSLA steel: Effect of thermal cycles on microstructure and mechanical properties.
Addit. Manuf. 2019, 27, 440–450. [CrossRef]
2. Rodrigues, T.A.; Duarte, V.; Miranda, R.M.; Santos, T.G.; Oliveira, J.P. Current status and perspectives on
wire and arc additive manufacturing (WAAM). Materials 2019, 12, 1121. [CrossRef] [PubMed]
3. Zakay, A.; Aghion, E. Effect of post-heat treatment on the corrosion behavior of AlSi10Mg alloy produced by
additive manufacturing. JOM 2019, 71, 1150–1157. [CrossRef]
4. Leon, A.; Shirizly, A.; Aghion, E.; Leon, A.; Shirizly, A.; Aghion, E. Corrosion behavior of AlSi10Mg alloy
produced by additive manufacturing (AM) vs. its counterpart gravity cast alloy. Metals 2016, 6, 148.
[CrossRef]
Metals 2020, 10, 98 9 of 10

5. Hosseini, V.A.; Högström, M.; Hurtig, K.; Bermejo, M.A.V.; Stridh, L.E.; Karlsson, L. Wire-arc additive
manufacturing of a duplex stainless steel: Thermal cycle analysis and microstructure characterization.
Weld. World 2019, 63, 975–987. [CrossRef]
6. Donoghue, J.; Antonysamy, A.A.; Martina, F.; Colegrove, P.A.; Williams, S.W.; Prangnell, P.B. The effectiveness
of combining rolling deformation with Wire–Arc Additive Manufacture on β-grain refinement and texture
modification in Ti–6Al–4V. Mater. Charact. 2016, 114, 103–114. [CrossRef]
7. Wu, B.; Pan, Z.; Ding, D.; Cuiuri, D.; Li, H.; Xu, J.; Norrish, J. A review of the wire arc additive manufacturing
of metals: Properties, defects and quality improvement. J. Manuf. Process. 2018, 35, 127–139. [CrossRef]
8. Ge, J.; Ma, T.; Chen, Y.; Jin, T.; Fu, H.; Xiao, R.; Lei, Y.; Lin, J. Wire-arc additive manufacturing H13 part:
3D pore distribution, microstructural evolution, and mechanical performances. J. Alloys Compd. 2019, 783,
145–155. [CrossRef]
9. Wang, L.; Xue, J.; Wang, Q. Correlation between arc mode, microstructure, and mechanical properties during
wire arc additive manufacturing of 316L stainless steel. Mater. Sci. Eng. A 2019, 751, 183–190. [CrossRef]
10. Bekker, A.C.M.; Jouke, C.V.; Giorgia, G. Challenges in assessing the sustainability of wire+ arc additive
manufacturing for large structures. In Proceedings of the Solid Freeform Fabrication Symposium–An
Additive Manufacturing Conference, Austin, TX, USA, 8–10 August 2016.
11. Cunningham, C.R.; Wikshåland, S.; Xu, F.; Kemakolam, N.; Shokrani, A.; Dhokia, V.; Newman, S.T. Cost
modelling and sensitivity analysis of wire and arc additive manufacturing. Procedia Manuf. 2017, 11, 650–657.
[CrossRef]
12. Caballero, A.; Ding, J.; Ganguly, S.; Williams, S. Wire + Arc Additive Manufacture of 17-4 PH stainless
steel: Effect of different processing conditions on microstructure, hardness, and tensile strength. J. Mater.
Process. Technol. 2019, 268, 54–62. [CrossRef]
13. Xu, X.; Ding, J.; Ganguly, S.; Diao, C.; Williams, S. Preliminary investigation of building strategies of maraging
steel bulk material using wire + arc additive manufacture. J. Mater. Eng. Perform. 2019, 28, 594–600.
[CrossRef]
14. Leon, A.; Aghion, E. Effect of surface roughness on corrosion fatigue performance of AlSi10Mg alloy produced
by selective laser melting (SLM). Mater. Charact. 2017, 131, 188–194. [CrossRef]
15. Zhang, C.; Li, Y.; Gao, M.; Zeng, X. Wire arc additive manufacturing of Al-6Mg alloy using variable polarity
cold metal transfer arc as power source. Mater. Sci. Eng. A 2018, 711, 415–423. [CrossRef]
16. Lin, Z.; Goulas, C.; Ya, W.; Hermans, M.J.M. Microstructure and mechanical properties of medium carbon
steel deposits obtained via wire and arc additive manufacturing using metal-cored wire. Metals 2019, 9, 673.
[CrossRef]
17. Gu, D. Laser Additive Manufacturing (AM): Classification, Processing Philosophy, and Metallurgical
Mechanisms. In Laser Additive Manufacturing of High-Performance Materials; Springer: Heidelberg/Berlin,
Germany, 2015; pp. 15–71.
18. Lockett, H.; Ding, J.; Williams, S.; Martina, F. Design for wire + arc additive manufacture: Design rules and
build orientation selection. J. Eng. Des. 2017, 28, 568–598. [CrossRef]
19. Derekar, K.S. A review of wire arc additive manufacturing and advances in wire arc additive manufacturing
of aluminium. Mater. Sci. Technol. 2018, 34, 895–916. [CrossRef]
20. Ghaffari, M.; Nemani, A.V.; Rafieazad, M.; Nasiri, A. Effect of solidification defects and HAZ softening on
the anisotropic mechanical properties of a wire arc additive-manufactured low-carbon low-alloy steel part.
JOM 2019, 71, 4215–4224. [CrossRef]
21. Gordon, J.; Hochhalter, J.; Haden, C.; Harlow, D.G. Enhancement in fatigue performance of metastable
austenitic stainless steel through directed energy deposition additive manufacturing. Mater. Des. 2019, 168.
[CrossRef]
22. Fadaei, A.; Mokhtari, H. Finite element modeling and experimental study of residual stresses in repair butt
weld of ST-37 plates. Iran. J. Sci. Technol. Trans. Mech. Eng. 2015, 39, 291–307.
23. Ron, T.; Levy, G.K.; Dolev, O.; Leon, A.; Shirizly, A.; Aghion, E. Environmental behavior of low carbon steel
produced by a wire arc additive manufacturing Process. Metals 2019, 9, 888. [CrossRef]
24. Shirizly, A.; Dolev, O. From wire to seamless flow-formed tube: Leveraging the combination of wire arc
additive manufacturing and metal forming. JOM 2019, 71, 709–717. [CrossRef]
25. Kaya, A.A.; Uzan, P.; Eliezer, D.; Aghion, E. Electron microscopical investigation of as cast AZ91D alloy.
Mater. Sci. Technol. 2000, 16, 1001–1006. [CrossRef]
Metals 2020, 10, 98 10 of 10

26. Elkaiam, L.; Hakimi, O.; Goldman, J.; Aghion, E. The effect of Nd on mechanical properties and corrosion
performance of biodegradable Mg-5%Zn alloy. Metals 2018, 8, 438. [CrossRef]
27. Itzhak, D.; Aghion, E. Corrosion behaviour of hot-pressed austenitic stainless steel in H2SO4 solutions at
room temperature. Corros. Sci. 1983, 23, 1085–1094. [CrossRef]
28. Itzhak, D.; Aghion, E. An anodic behaviour study of an analogical sintered system of austenitic stainless
steel in H2SO4 solution. Corros. Sci. 1984, 24, 145–149. [CrossRef]
29. Kafri, A.; Ovadia, S.; Goldman, J.; Drelich, J.; Aghion, E. The suitability of Zn–1.3%Fe alloy as a biodegradable
implant material. Metals 2018, 8, 153. [CrossRef]
30. Gerengi, H.; Uygur, I.; Solomon, M.; Yildiz, M.; Goksu, H. Evaluation of the inhibitive effect of Diospyros
kaki (Persimmon) leaves extract on St37 steel corrosion in acid medium. Sustain. Chem. Pharm. 2016, 4,
57–66. [CrossRef]
31. Tayanç, M.; Aytaç, A.; Bayram, A. The effect of carbon content on fatigue strength of dual-phase steels.
Mater. Des. 2007, 28, 1827–1835. [CrossRef]
32. Campbell, E.; Flake, C. Elements of Metallurgy and Engineering Alloys; Chapter 14, Fatigue; ASM International:
Cleveland, OH, USA, 2008.
33. Sonsino, C.M. Course of SN-curves especially in the high-cycle fatigue regime with regard to component
design and safety. Int. J. Fatigue 2007, 29, 2246–2258. [CrossRef]
34. Naito, T.; Ueda, H.; Kikuchi, M. Fatigue behavior of carburized steel with internal oxides and nonmartensitic
microstructure near the surfsace. Metall. Trans. A 1984, 15, 1431–1436. [CrossRef]
35. Mutoh, Y.; Tanaka, K. Fretting fatigue in several steels and a cast iron. Wear 1988, 125, 175–191. [CrossRef]

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