metals

Article
Formation of SUS304/Aluminum Alloys Using Wire
and Arc Additive Manufacturing
Zhizhuang Hao 1,2 , Sansan Ao 1,2, *, Yangchuan Cai 1,2 , Wei Zhang 1,2 and Zhen Luo 1,2
1 School of Materials Science and Engineering, Tianjin University, Tianjin 300350, China;
caikongerbanhzz@163.com (Z.H.); 18622265848@163.com (Y.C.); zhang.vv@foxmail.com (W.Z.);
lz_tju@163.com (Z.L.)
2 Tianjin Key Laboratory of Advanced Joining Technology, Tianjin University, Tianjin 300350, China
* Correspondence: ao33@tju.edu.cn; Tel.: +86-136-7215-9533




Received: 2 July 2018; Accepted: 26 July 2018; Published: 30 July 2018


Abstract: In this study, wire and arc additive manufacturing (WAAM) was used to form
SUS304/aluminum alloys. The buildup wall was well shaped using a pulse current consisting
of a base current of 150 A and peak current of 200 A and a 0.2 m/min travel speed. Metallographic
observation revealed that the original grains were columnar grains and transformed into equiaxed
grains in the top area. The increased content of alloying elements in the fused layer improved the
hardness of the buildup wall. The buildup wall formed using pulsed current exhibited improved
anti-electrochemical corrosion performance when compared with that formed using constant current.
The tensile strength of the alloy decreased but its elongation increased compared with those of
Fe-Al alloys. The tensile fracture along the fusing direction was plastic fracture. However, the tensile
fracture perpendicular to the fusing direction consisted of a combination of plastic and brittle fracture.

Keywords: wire and arc additive manufacturing; SUS 304/aluminum alloys; mechanical properties;
electrochemical corrosion

1. Introduction
Fe-Al alloy has been researched since the early 20th century due to the excellent oxidation and
sulfidation resistance, high temperature strength, and creep resistance [1]. These excellent properties make
some materials, which require thermal and corrosion resistance, could be replaced by Fe-Al alloy [2].
In recent years, as a new manufacturing method, additive manufacturing (AM) has been applied
in many industries because of its excellent advantages, such as high efficiency, simple equipment,
low cost, and convenient design [3]. Over the past 15 years, there has been a sharp increase in the
demand for AM technology to make complex parts [4]. To date, additive manufacturing is used to
make a variety of metals, such as aluminium alloy [5], titanium alloy [6], and steel [7]. For metal
additive manufacturing, it can be classified according to the kind of raw materials. They are generally
powder based process, such as laser additive manufacturing (LAM) [8] and selective laser melting
(SLM) [9]; or, wire based process, such as wire and arc additive manufacturing [10]. Although powder
based process has high manufacturing precision, pores are produced in the manufacturing process and
high cost [11–13], whose defect must be avoided in Fe-Al alloy. On the contrary, the completely dense
materials could be manufactured by wire and arc additive manufacturing (WAAM) using appropriate
parameters. In addition, with the same composition, the wire is cheaper than powder.
The WAAM process usually uses single feed wire and produces a deposited structure of the same
composition as the wire. Recently, the WAAM using gas tungsten arc welding (GTAW) process has been
used to manufacturing binary phase intermetallic materials, such as gamma titanium aluminide [14]
and Fe3 Al based iron aluminide [15]. Chen et al. [15] completed the preparation of Fe-Al alloy

Metals 2018, 8, 595; doi:10.3390/met8080595 www.mdpi.com/journal/metals

Metals 2018, 8, 595 2 of 12

by WAAM process, and made an in-depth study of its microstructure, chemical composition, and
mechanical properties. However, the elongation of the formed material is only 3.5%. Pan et al. [16]
fabricated the Fe-Al functionally graded material while using WAAM with pour elongation of 2.35%.
But, when considering the brittle in room temperature of Fe-Al alloy [17], it is very difficult
to manufacture this material, which has caused a sharp increase in the cost of manufacturing [18].
Studied are urgently needed to improve the room temperature ductility of the Fe-Al alloy in order
to reduce manufacturing cost. To improve the room temperature ductility of Fe-Al alloy, some alloy
elements are often added in the manufacturing process, such as boron [19], chromium [20], cerium [21],
carbon, niobium, and titanium [22]. The principle that these alloy elements can improve the room
temperature ductility is to enhance the grain boundary strength. In addition, the chromium can change
the slip from coarse straight slip to a fine wavy slip. In this study, 304 stainless steel (SUS 304) wire
and 4043 aluminum alloy (AA 4043) wire were fused together through WAAM to form a new Fe-Al
alloy. The chromium in 403 stainless steel will enhance the grain boundary strength of the alloy, so as
to enhance the room temperature ductility.
The main content of this study is the manufacturing of Fe-Al alloy by WAAM using SUS 304
wire and AA 4043 wire for reducing the room temperature brittleness. Meanwhile, the microstructure,
micro hardness, tensile properties, and electrochemical corrosion resistance of Fe-Al alloy were
further studied.

2. Experimental Section

2.1. Materials and Fabrication Process

The robot system that was used during the experiments and a representative molded product
are shown in Figure 1a. In order to meet the requirements, a new wire feed fixture adapted to the
experimental conditions was designed. The robot system was a Panasonic YC—400TX industrial robots
(Panasonic Corporation, Osaka, Japan) with a Panasonic TIG welder (Panasonic Corporation, Osaka, Japan).
The tungsten pole with diameter of 4 mm was negative during the manufacturing process (DCSP).
Two standard welding wires with diameters of 1.2 mm, 304 stainless steel, and 4043 aluminum alloy
wire, were simultaneously fed into the welding pool. Low carbon steel (250 mm × 150 mm × 8 mm) was
selected as the base metal because of its excellent welding performance, and the base metal was preheated
to 300 ◦ C before the start of the experiment to improve the wettability [23]. The chemical constituents of
the three materials that were used in the experiment are listed in Table 1. Pure argon (99.99%) was used as
the inert gas for the WAAM process and the gas flow was 20 L/min. Figure 1b shows the as-fabricated
wall after completion of the entire welding process. The width and height of the wall with 10 layers were
approximately 8 and 31 mm, respectively, with some substrate distortion being present. The heights of
both ends were lower than that of the middle position. To overcome this issue, more precise control of the
inter-layer temperature would be required.

Table 1. Chemical constituents of two wires and base metal.

wt.% C Mn P S Si Cr Ni Cu Al Fe
SUS 304 ≤0.08 ≤2.0 ≤0.045 ≤0.03 ≤1.00 ≤18.0 ≤8.0 - - Balance
AA 4043 - ≤0.05 - - ≤6.0 - - ≤0.3 Balance ≤0.8
Low carbon steel ≤0.22 ≤1.4 ≤0.045 ≤0.05 ≤0.35 - - - Balance -
Metals 2018, 8, 595 3 of 12
Metals 2018, 8, x FOR PEER REVIEW 3 of 12

Figure 1. (a) Robot system and (b) representative molded product.

Figure 1. (a) Robot system and (b) representative molded product.

The experimental parameters are listed in Table 2. Two currents were used in the experiment, a
The current
constant experimental
(CC) ofparameters
150 A, and are a 2 listed
Hz pulsein Table 2. Two
current (PC) currents were
with a base used of
current in 150
the A,
experiment,
and peak
a constant current (CC) of 150 A, and a 2 Hz pulse current (PC) with a base current of
current of 200 A. The objective of these experiments was to explore the effect of the experimental 150 A, and peak
current of 200
parameters on A.theThe objective
quality of theof these experiments
formation. was to explore
The inter-layer the effect
temperature of the
in the experimental
experiment was
parameters on the quality of the formation. The inter-layer temperature in the
controlled at 400 °C by automatic temperature measuring device in order to prevent the generation experiment was
controlled ◦ C by automatic temperature measuring device in order to prevent the generation
at 400 The
of cold cracking. FLIR T420 infrared thermal imager (FLIR Systems, Inc., Wilsonville, AL, USA)
of cold cracking. The
monitored the temperature FLIR T420of infrared thermallayer.
the deposited imager
When(FLIRthe
Systems, Inc., Wilsonville,
temperature is below 400AL, °C,
USA)a
monitored the temperature of the deposited layer. When the temperature is below 400 ◦ C, a subsequent
subsequent deposit was made. This method has been shown to improve the room-temperature
deposit was
ductility of Femade. This method has been shown to improve the room-temperature ductility of
3Al-based iron aluminides [16].
Fe3 Al-based iron aluminides [16].
Table 2. Experimental parameters.
Table 2. Experimental parameters.
Wire Feed Speed (mm/s−1) Welding Speed Arc Length
Number Wire Feed Speed (mm/s −1 ) Current Type
Welding Speed Arc (mm)
Length
Number SUS 304 AA 4043 Current Type (m/min −1)

SUS 304 AA 4043 (m/min−1 ) (mm)

1 10 10 PC 0.2 5
21 10 10 10 10 PCPC 0.3
0.2 55
2 10 10 PC 0.3 5
33 10 10 10 10 PCPC 0.4
0.4 5
5
44 10 10 10 10 CCCC 0.2
0.2 55
55 10 10 10 10 CCCC 0.3
0.3 55
6 10 10 CC 0.4 5
6 10 10 CC 0.4 5

2.2. Material
2.2. Material Characterization
Characterization
The extraction
The extractionlocations for various
locations material
for various samplessamples
material are shown in Figure
are shown2a.inThe metallographic
Figure 2a. The
specimens werespecimens
metallographic prepared using wire cutting
were prepared and
using then
wire sanded
cutting andusing
thensandpaper
sanded using from 400# to 2000#.
sandpaper from
For the etchant, 50% aqua regia was used because of the excellent corrosion resistance
400# to 2000#. For the etchant, 50% aqua regia was used because of the excellent corrosion resistance of the alloy,
and
of thethe etching
alloy, and time was approximately
the etching 5 s. The microstructure
time was approximately was examined
5 s. The microstructure using the Olympus
was examined using the
optical microscope (Olympus, Tokyo, Japan), and the macro chart of the fused
Olympus optical microscope (Olympus, Tokyo, Japan), and the macro chart of the fused layer layer was obtained
was
using a stereoscopic microscope VHX-5000 (Keyence, Osaka, Japan). The grain
obtained using a stereoscopic microscope VHX-5000 (Keyence, Osaka, Japan). The grain size was size was measured
according to
measured the ASTM
according to E112-10
the ASTM standard
E112-10to show the effect
standard to showof grain size on
the effect of properties.
grain size onVickers micro
properties.
hardnessmicro
Vickers measurements were performed
hardness measurements across
were the fusion
performed line the
across using a MHV-10Z
fusion line usinghardness tester
a MHV-10Z
(Changzhou Sanfeng Instrument Technology Co., Ltd., Changzhou, China) at
hardness tester (Changzhou Sanfeng Instrument Technology Co., Ltd., Changzhou, China) at a loada load of 300 N and
0.2300
of mmNintervals
and 0.2 while using a 15s
mm intervals hold
while time.a The
using element
15s hold distribution
time. The element across the fusionacross
distribution line was
the
measured using scanning electron microscopy SEM Hitachi SU1510 (Hitachi, Tokyo,
fusion line was measured using scanning electron microscopy SEM Hitachi SU1510 (Hitachi, Tokyo, Japan) coupled
with
Japan) energy-dispersive X-ray spectrometry
coupled with energy-dispersive X-ray(EDAX Inc., Draper,
spectrometry (EDAXUT,Inc.,
USA). Specific
Draper, detection
Utah, USA). location
Specific
of hardness, EDS and microstructure are shown in Figure 2b.
detection location of hardness, EDS and microstructure are shown in Figure 2b.
A cross section of the XOZ plane was examined to determine the electrochemical corrosion with
area of 1 cm2. The electrochemical corrosion property was studied using LK3200A electrochemical
detection system (Lanlike Chemical Electronic High-Tech Co. Ltd., Tianjin, China). The test was
Metals 2018, 8, 595 4 of 12

MetalsA cross
2018, 8, xsection the XOZ
ofREVIEW
FOR PEER plane was examined to determine the electrochemical corrosion4 with of 12
area of 1 cm2 . The electrochemical corrosion property was studied using LK3200A electrochemical
detection system
conducted (Lanlike
in 3.5 wt% NaCl Chemical
solution Electronic High-Tech Co.
at room temperature. Ltd., Tianjin,
To stabilize China). The
the potential, the test was
conducted
started afterinthe
3.5specimen
wt% NaCl wassolution
soakedatinroom temperature.
the 3.5 To stabilize
wt% NaCl solution the potential,
for about 10 min. Thethe test was
scanned
started after the specimen was soaked in the 3.5 wt% NaCl solution for
area of the potential was from −1.0 V to 1.0 V, and the scanning speed was 0.01 V/s. about 10 min. The scanned
area The
of thetensile
potential
simple fromis−1.0
was size V to Figure
shown 1.0 V, and
2c, the scanningtospeed
according ASTM was 0.01
E8. V/s.
The tensile tests were
The tensile
conducted simple
thrice sizeparameter
at each is shown Figure
before2c,taking
according
the to ASTM value
average E8. Theastensile teststest
the final weremagnitude.
conducted
thrice at each
Scanning parameter
electron before was
microscope taking theto
used average
observevalue
the as the final test magnitude.
micro-morphology Scanning
of impact electron
fractures after
microscope
tensile test. was used to observe the micro-morphology of impact fractures after tensile test.

Figure 2. (a) Specimen extraction locations for analyses of the elemental distribution, hardness,
Figure 2. (a) Specimen extraction locations for analyses of the elemental distribution, hardness,
microstructure, electrochemical corrosion, and tensile properties; (b) the test location for hardness
microstructure, electrochemical corrosion, and tensile properties; (b) the test location for hardness and
and microstructure in plane XOZ; and, (c) specific dimensions of tensile samples.
microstructure in plane XOZ; and, (c) specific dimensions of tensile samples.

3. Results and Discussion

3. Results and Discussion
3.1.
3.1. Quality
Quality of
of Fabrication
Fabrication and
and Phase
Phase Characterization
Characterization
A macro
A macro chart
chart ofof a several
several weld cross-section
cross-section for all the welding parameters
parameters is presented in
Figure 3. Metallic
Metallic exfoliation
exfoliation was
was observed
observed in in Figure
Figure 3c,e,f,
3c,e,f, and
and the
the area of exfoliation increasing
with increasing travel speed. Especially
Especially nearnear the
the fusion
fusion line,
line, the difference between the base metal
compositions results in a high stress concentration. Therefore, metal exfoliation
and cladding layer compositions
was mainly detected near the fusion line. This This finding
finding isis most likely related to the compositional
changes that
thatarearenear
nearthethe
fused line.line.
fused In Figure 4, the elemental
In Figure contentscontents
4, the elemental changed faster withfaster
changed increasing
with
travel speed
increasing nearspeed
travel the fused
near line. Therefore,
the fused the composition
line. Therefore, changed substantially
the composition near the fused
changed substantially near
line,fused
the and the
line,internal
and thestress correspondingly
internal increased.
stress correspondingly A slower
increased. A travel
slowerspeed
travelresults
speed in a slower
results in a
coolingcooling
slower rate, which
rate, most
whichlikely
mostreduces the stress
likely reduces thein the material.
stress Therefore,
in the material. with increasing
Therefore, travel
with increasing
speed,speed,
travel the areatheofarea
exfoliation increased,
of exfoliation and exfoliation
increased, was even
and exfoliation was observed in areas
even observed in that
areasare
thataway
are
from the
away fused
from theline (Figure
fused line 3f). Considering
(Figure the existence
3f). Considering the of exfoliation
existence under several
of exfoliation parameters,
under several
the remaining
parameters, theparameters are used inare
remaining parameters subsequent experiments
used in subsequent of CC 0.2 of
experiments m/min,
CC 0.2CC 0.3 m/min,
m/min, CC 0.3
m/min, and PC 0.2 m/min. In the following paper, CC 0.2 m/min, CC 0.3 m/min, and PC 0.2 m/min
are, respectively, represented by I, II, and III.
Metals 2018, 8, 595 5 of 12

and PC 0.2 m/min. In the following paper, CC 0.2 m/min, CC 0.3 m/min, and PC 0.2 m/min are,
respectively, represented
Metals 2018, 8, x FOR PEER by I, II, and III.
REVIEW 5 of 12

Metals 2018, 8, x FOR PEER REVIEW 5 of 12

Figure 3. Macro morphology of single bead in different experimental parameters: (a) CC 0.2 m/min;
Figure (b)3.CCMacro morphology
0.3 m/min; (c) CC 0.4ofm/min;
single(d) beadPC in0.2different
m/min; (e)experimental
PC 0.3 m/min;parameters:
and (f) PC 0.4(a) CC 0.2 m/min;
m/min.
(b) CC 0.3 m/min; (c) CC 0.4 m/min; (d) PC 0.2 m/min; (e) PC 0.3 m/min; and (f) PC 0.4 m/min.
Figure
The EDS 3. Macro
resultsmorphology
obtained are of single
presentedbead in in different
Figure 4.experimental
For all of the parameters:
specimens, (a) CC
the 0.2
leftm/min;
side of the
(b)line
CC 0.3 m/min; (c) CC 0.4 m/min; (d)right
PC 0.2 m/min; (e)fusion
PC 0.3 m/min; and (f)fused
PC 0.4layer.
m/min.
The EDS results obtained are presented in Figure 4. For all of the specimens, the leftcontent
fusion was the base metal, and the side of the line was the The side of the
fusionofline
all thewas
The EDS
elements
the basechanged
metal, across
and theright
the fusionside line.ofThe
the relative
fusion Felinecontent
was wasfused
the reduced upon
layer. Thecrossing
content of
the fusion lineresults
from obtained
the base metalare presented
to the fused in Figure
layer.4.On Forthe
all contrary,
of the specimens,
the relativethe Al,
left Cr,
sideandof the
Ni
all thefusion
elementsline changed
was the upon
base across
metal, theandfusion line.side
thefusion
right Theofrelative
thethe Fe content
fusion wasfused
reduced upon crossing the
contents increased crossing the line from base line
metal wasto the
the fused layer.
layer. TheThe content
relative
fusionof line
all from
the the base
elements metalacross
changed to thethe fused
fusion layer.
line. On
The the contrary,
relative Fe the relative
content was Al, Cr,
reduced andcrossing
upon Ni contents
C content negligibly changed upon crossing the fusion line, and the C content was very low.
increased upon
the fusion crossing
line from the
the fusion
base metalline tofrom
the the
fused base
layer. metal
On to
the the fused
contrary,
The C content of low carbon steel (~0.2%) and 304 stainless steel is lower than the content of layer.
the The
relative relative
Al, Cr, andC the
content
Ni
contents
negligibly increased
changed upon
other elements, upon crossing
which crossing
explains the the
the low fusion
fusion line from
line, and
C content the base
theofCthe
in all metal
content to
specimens. the
was very fused
Al, Cr, layer.
low. The relative
and Ni were only
C
Thecontent
present innegligibly
C content two types changed
of low wire.upon
of carbon crossing
steel
Therefore, thethe
(~0.2%) fusion
and
Al, Cr, 304 line,
and and
stainless
Ni the C
contents content
steelwere wasin
is lower
low very
thelow.
than the metal.
base content of
The C content of low carbon steel (~0.2%) and 304
the other elements, which explains the low C content in all of the specimens. Al, Cr, and
Additionally, in the fused layer, with increasing distancestainless
from steel
the is lower
fusion than
line, the the content
content of of thewere
Ni
these
other
three elements,
elements which explainsand the then
low Ctendedcontent in all of constant.
the specimens. Al,content
Cr, and Ni wereinonly
only present in twofirst typesincreased
of wire. Therefore, the toAl,remain
Cr, and Ni contents The Fe were lowisin lower
the base 304metal.
present
stainless inin two
steel types of wire. Therefore, the Al, Cr, and Ni contents were low in the base metal.
Additionally, thethan
fusedin low
layer,carbon
withsteel. Therefore,
increasing the Fefrom
distance content
thedecreases
fusion line, uponthecrossing
contentthe fusionthree
of these
Additionally,
line from the base in the fused
metal layer,
into with increasing
the fused distancecontent
layer. The specific from the fusion
of all line, the
elements content
is shown in of these
Table 3.
elements
threefirst increased
elements and thenand
first increased tended then to remain
tended constant.
to remain The FeThe
constant. content is lower
Fe content in 304
is lower in stainless
304
steel stainless
than in low steelcarbon
than in steel. Therefore,
low carbon the Fe content
steel. Therefore, the Fedecreases upon crossing
content decreases upon crossingthe fusion line from
the fusion
the base metal into the fused layer. The specific content of all elements
line from the base metal into the fused layer. The specific content of all elements is shown in Table 3. is shown in Table 3.

Figure 4. Energy-dispersive X-ray spectrometry (EDS) results: (a) the scanning positon; (b) I: CC 0.2
m/min; (c) II: CC 0.3 m/min; and, (d) III: PC 0.2 m/min.

Figure 4. Energy-dispersive X-ray spectrometry (EDS) results: (a) the scanning positon; (b) I: CC 0.2
Figure 4. Energy-dispersive X-ray spectrometry (EDS) results: (a) the scanning positon; (b) I: CC 0.2 m/min;
m/min; (c) II: CC 0.3 m/min; and, (d) III: PC 0.2 m/min.
(c) II: CC 0.3 m/min; and, (d) III: PC 0.2 m/min.
Metals 2018, 8, 595 6 of 12
Metals 2018, 8, x FOR PEER REVIEW 6 of 12

Table 3. Content of all elements: I (CC 0.2 m/min), II (CC 0.3 m/min) and III (PC 0.2 m/min).
Table 3. Content of all elements: I (CC 0.2 m/min), II (CC 0.3 m/min) and III (PC 0.2 m/min).

wt.% I I II II III III

Wt.%
BaseBase MetalFused
Metal Fused
LayerLayerBaseBase
MetalMetalFused
Fused
LayerLayerBaseBase
MetalMetal
FusedFused
LayerLayer
Cr
Cr 1.861.86 13.9113.91 2.092.09 8.92 8.92 1.65 1.65 10.1410.14
Ni
Ni 0.930.93 3.37 3.37 1.16 1.16 2.64 2.64 0.94 0.94 3.17 3.17
Fe 94.12 58.96 93.46 59.17 94.16 60.65
Fe
Al 94.121.47 58.9621.16 93.461.64 59.1726.41 94.161.61 60.6523.33
Al
C 1.470.63 21.160.51 1.640.67 26.410.54 1.61 0.60 23.33 0.50
C
Si 0.630.99 0.512.09 0.670.98 0.54 2.32 0.60 1.04 0.50 2.21
Si 0.99 2.09 0.98 2.32 1.04 2.21
XRDdetection
XRD detectionisis used
used to
to study
study the
the phases
phases that
that appear
appear in
in the
the manufacturing
manufacturing process
process and and the
the
results are
results areshown
shownininFigure 5. The
Figure mainmain
5. The phases is the intermetallic
phases compound
is the intermetallic Al1.1 Ni0.9 .Al
compound The positions
1.1Ni0.9. The
of the peaks in the XRD results of all samples are the same. This indicates that with
positions of the peaks in the XRD results of all samples are the same. This indicates that with the different
the
parameters,
different the typesthe
parameters, of phase
types in
of the
phasedeposit
in thehave not have
deposit changed.
not changed.

Figure5.
Figure 5. XRD
XRD results:
results: II (CC
(CC 0.2
0.2 m/min),
m/min), II
II (CC
(CC 0.3
0.3 m/min)
m/min)and
andIII
III(PC
(PC0.2
0.2m/min).
m/min).

3.2.
3.2. Microstructure
Microstructure
The
The microstructures
microstructuresof ofthe
thespecimens
specimensare areshown
shownininFigure
Figure6.6.Near
Nearthethe
substrate, thethe
substrate, growth
growth of
columnar
of columnar grains
grainsalong thethe
along direction
direction perpendicular
perpendicular totothe
thesubstrate
substratewaswasobserved
observedbecause
becauseof of the
the
maximum temperature gradient, as shown in the Figure 6a, c, e. As observed
maximum temperature gradient, as shown in the Figure 6a,c,e. As observed in the Figure 4b,d,f,in the Figure 4b, d, f,
the
the grains
grains were
were transformed
transformed into
into equiaxed
equiaxedgrains
grainsin
inthe
thetop
topregions.
regions.In Inthe
thearea
areanear
nearthe
thefusion
fusionline,
line,
the
the temperature gradient along the Z direction was maximum; therefore, the driving force for the
temperature gradient along the Z direction was maximum; therefore, the driving force for the
growth
growth ofof columnar
columnar grains
grains was
was the
the maximum
maximum along
alongthe
theZZdirection.
direction. OnOnthe
thetop
topof
ofthe
thecladding
claddinglayer,
layer,
the
the temperature
temperature gradients
gradients in
in each
each direction
direction were
were similar, and equiaxed
similar, and equiaxed grains
grains thus
thus began
began toto form.
form.
Metals 2018, 8, 595 7 of 12

Metals 2018, 8, x FOR PEER REVIEW 7 of 12

Figure 6. Microstructures of specimens I (a,b: CC 0.2 m/min), II (c,d: CC 0.3 m/min), and III (e,f: PC
Figure 6. Microstructures of specimens I (a,b: CC 0.2 m/min), II (c,d: CC 0.3 m/min), and III
0.2 m/min).
(e,f: PC 0.2 m/min).
The sizes of the columnar and equiaxed grains are listed in Table 4, and for the columnar, the
The
largest sizes
size of thegrain
of single columnar and equiaxed
was measured. grains areinlisted
The difference grainin Table
size 4, and
between forand
first thesubsequent
columnar,
the largest size of single grain was measured. The difference in grain size between
layers was assumed to be small enough to be neglected, thus allowing for considering them as a first and subsequent
layers
valuablewas assumed
factor to bevariations
to explain small enough to be neglected,
in mechanical thus
resistance. allowing
Grain for considering
sizes decrease them as
with increasing
atravel
valuable factor to explain variations in mechanical resistance. Grain sizes decrease
speed (I and II), which is related to less heat accumulation. The same area will produce less with increasing
travel
heat forspeed (I and
a faster II), which
travel speed. isForrelated to less heat
an identical travelaccumulation.
speed, the sizeThe of same area will
two grains produce
is larger whenless
a
heat for acurrent
constant faster travel speed.
is applied ForIII),
(I and an which
identical travel
is also speed,
related size heat
to the less of two
inputgrains
duringis larger when
welding. In
apulsed
constant currentthe
welding, is applied (I anddwell
peak current III), which
time is is also related
shorter, andtothe
thecooling
less heattime
input during
will welding.
be shortened.
In pulsed welding,
Therefore, the peak
the nucleation current dwell
of equiaxed grainstime
beganis shorter,
before theandcolumnar
the cooling timegrew
grains will too
be shortened.
large. The
Therefore,
size of the the nucleation
equiaxed of also
grains equiaxed grainsbecause
decreased began before
of thethe columnar
shorter coolinggrains
time.grew
Graintoorefinement
large. The will
size
of the equiaxed grains also decreased because of the shorter cooling
have an impact on mechanical properties and relevant analysis is given below. time. Grain refinement will have
an impact on mechanical properties and relevant analysis is given below.
Metals 2018, 8, x FOR PEER REVIEW 8 of 12

Metals 2018, 8, 595 8 of 12

Table 4. Size of columnar and equiaxed grains: I (CC 0.2 m/min), II (CC 0.3 m/min), and III (PC 0.2
m/min).
Table 4. Size of columnar and equiaxed grains: I (CC 0.2 m/min), II (CC 0.3 m/min), and III (PC 0.2 m/min).
Grain Size (μm)
Samples Grain Size (µm)
Samples Equiaxed Grains Columnar Grains
I Equiaxed
239.1 Grains Columnar Grains
267.8
II I 114.8 239.1 267.8 105.5
III II 192 114.8 105.5 256.7
III 192 256.7

3.3. Electrochemical Corrosion

3.3. Electrochemical Corrosion
Polarization curves of the specimens are presented in Figure 7. The electrolyte solution for the
Polarizationcorrosion
electrochemical curves ofexperiments
the specimens wasare3.5%presented in Figure
NaCl solution. 7. type
The The electrolyte solutionaffected
of current greatly for the
electrochemical
the electrochemical corrosion experiments
corrosion was 3.5%
of the fusion layer.NaCl solution. The
The corrosion type of
potential ofcurrent greatly
the curve I andaffected
II was
the electrochemical corrosion of the fusion layer. The corrosion potential of
closer to the negative direction than curve III, which indicates that specimens prepared using the curve I andaIIpulse
was
closer to the negative direction than curve III, which indicates that specimens prepared
current are less susceptible to corrosion than those that were prepared using a constant current [24]. using a pulse
current
In termsare of less susceptible
corrosion to corrosion
current, than prepared
the specimen those thatusing
were prepared using awas
a pulse current constant
smallercurrent [24].
than that
In terms of corrosion current, the specimen prepared using a pulse current was smaller
prepared using a constant current, indicating that the using of the pulse current resulted in a slower than that
prepared
corrosion using a constant
rate. This findingcurrent,
is relatedindicating that the
to the relative using of
content of the
the alloying
pulse current resulted
elements. The in a slower
relative Ni
corrosion rate. This finding is related to the relative content of the alloying elements.
and Cr contents were higher in the specimens that were fabricated using pulse current than constant The relative Ni
and Cr contents were higher in the specimens that were fabricated using pulse current
current. Ni and Cr exhibit excellent electrochemical corrosion in the natural environment. Therefore, than constant
current.
the Ni andelectrochemical
improved Cr exhibit excellent electrochemical
corrosion of the buildupcorrosion in the natural
wall fabricated environment.
using pulse currentTherefore,
may be
attributed to the high Ni and Cr contents. In summary, the molded products thatmay
the improved electrochemical corrosion of the buildup wall fabricated using pulse current be
were
attributed to the high Ni and Cr contents. In summary, the molded products
manufactured while using a pulse current exhibited improved resistance to electrochemical that were manufactured
while using a pulse current exhibited improved resistance to electrochemical corrosion.
corrosion.

Figure
Figure7.7. Polarization curvesofof
Polarization curves specimens:
specimens: I (CC
I (CC 0.2 m/min),
0.2 m/min), II (CCII0.3(CC 0.3 m/min),
m/min), and0.2IIIm/min).
and III (PC (PC 0.2
m/min).
3.4. Micro Hardness
3.4. Micro Hardness
The hardness curves measured along the centerline of a single weld are presented in Figure 8.
The hardness
The direction curves measured
of measurement alongthe
was from thetop
centerline of a single
of the cladding weld
layer are base
to the presented in Figure
material, and the 8.
The direction of measurement was from the top of the cladding layer to the
distance between measurements was 0.2 mm. The hardness of the deposited layer was higher than that base material, and the
distance
of the basebetween
metal. measurements
The increasing was 0.2hardness
of the mm. Thevalueshardness of thetodeposited
is related layer alloying
the increasing was higher than
element
that of the base metal. The increasing of the hardness values is related to the
contents. The relative Cr, Ni, and Al contents were greater in the cladding layer. It is related to the increasing alloying
element
generation contents. Thesuch
of phase, relative
as AlCr, Ni, and Al contents were greater in the cladding layer. It is
1.1 Ni0.9 . The dispersion of these phases in the material resulted in
related to thestrengthening
precipitation generation of of phase, such as wall.
the buildup Al1.1Ni 0.9. The dispersion of these phases in the material
However, according to reports in the references [1]
resulted in precipitation strengthening of the
and [15,16], the main strengthening mode of this material buildup wall. However,
is solid solution according to reports
strengthening, mainlyin the
the
references [1] and [15,16], the main strengthening mode of this material
entry of aluminum atoms into the crystal of iron. As a whole, the hardness of the three samples is is solid solution
strengthening,
II > III > I, whichmainly the toentry
is related of aluminum
the difference atoms
in grain size. into the crystal
As shown of 3,iron.
in Table grainAssizea in
whole,
samplethe II
Metals 2018, 8, x FOR PEER REVIEW 9 of 12
Metals 2018, 8, 595 9 of 12
hardness of the three samples is II > III > I, which is related to the difference in grain size. As shown
in Table 3, grain size in sample II is smallest in all three samples. The smaller the grain size, the
is smallest
higher in all three samples.
the mechanical The
properties ofsmaller the grain
the material willsize, the higher the
be. Therefore, the hardness
mechanical
of properties of the
sample II is the
material
highest. will be. Therefore, the hardness of sample II is the highest.

Figure 8. Hardness curves measured along the centerline: I (CC 0.2 m/min), II (CC 0.3 m/min), and
Figure 8. Hardness curves measured along the centerline: I (CC 0.2 m/min), II (CC 0.3 m/min), and III
III (PC 0.2 m/min).
(PC 0.2 m/min).

3.5. Tensile Properties

3.5. Tensile Properties
The room-temperature tensile properties of three samples are summarized in Table 5. Tensile
The room-temperature tensile properties of three samples are summarized in Table 5.
testing was applied in both the Y and Z directions to demonstrate the connection between the
Tensile testing was applied in both the Y and Z directions to demonstrate the connection between the
orientation and tensile properties. The results indicate that the tensile strength in the Z direction
orientation and tensile properties. The results indicate that the tensile strength in the Z direction was
was always less than that in the Y direction. The main reason for this phenomenon is that the
always less than that in the Y direction. The main reason for this phenomenon is that the stretching
stretching along the Z direction has more interfaces between the adjacent layers, which are weak
along the Z direction has more interfaces between the adjacent layers, which are weak positions during
positions during tensile [25,26]. Each data point represents the average of three samples to reduce
tensile [25,26]. Each data point represents the average of three samples to reduce the experimental error.
the experimental error. The tensile strength only slightly decreased when compared with that of 304
The tensile strength only slightly decreased when compared with that of 304 stainless steel (520 MPa),
stainless steel (520 MPa), which indicates that this molded product could be applied in some areas.
which indicates that this molded product could be applied in some areas. However, the mechanical
However, the mechanical properties in the Z direction were worse than those in the Y direction,
properties in the Z direction were worse than those in the Y direction, which requires adjustment
which requires adjustment of the process parameters and is the subject of an on-going investigation.
of the process parameters and is the subject of an on-going investigation. In terms of elongation,
In terms of elongation, the elongation of the obtained Fe-Al alloy has been improved when
the elongation of the obtained Fe-Al alloy has been improved when compared to that made from pure
compared to that made from pure iron wire and pure aluminum wire using WAAM [16]. The
iron wire and pure aluminum wire using WAAM [16]. The results show that the room temperature
results show that the room temperature brittleness of Fe-Al alloy can be improved by adding alloy
brittleness of Fe-Al alloy can be improved by adding alloy elements. The main reason for the difference
elements. The main reason for the difference in tensile strength of different samples is that the grain
in tensile strength of different samples is that the grain size is different. The grain size of sample II is the
size is different. The grain size of sample II is the smallest, so the tensile strength is the largest. As
smallest, so the tensile strength is the largest. As can be seen from Figure 8 and Table 5, the hardness
can be seen from Figure 8 and Table 5, the hardness varies by about 50%, and the strength varies by
varies by about 50%, and the strength varies by about 5%. The reason for this phenomenon can be
about 5%. The reason for this phenomenon can be attributed to the difference in measurement scale.
attributed to the difference in measurement scale. For hardness testing, it is only done in a local area.
For hardness testing, it is only done in a local area. For the tensile testing, it shows the overall
For the tensile testing, it shows the overall performance of the sample.
performance of the sample.

Table 5. Room-temperature tensile properties: I (CC 0.2 m/min), II (CC 0.3 m/min), and III (PC 0.2
m/min).

Number Tensile Direction Y direction Z direction

Ultimate tensile strength (MPa) 488 ± 21 458 ± 15
I 0.2% yield strength (MPa) 440 ± 12 392 ± 10
Elongation (%) 10.2 ± 0.1 9.9 ± 0.1
II Ultimate tensile strength (MPa) 515 ± 15 485 ± 14
Metals 2018, 8, 595 10 of 12

Table 5. Room-temperature tensile properties: I (CC 0.2 m/min), II (CC 0.3 m/min), and III (PC 0.2 m/min).

Number Tensile Direction Y direction Z direction

Ultimate tensile strength (MPa) 488 ± 21 458 ± 15
I 0.2% yield strength (MPa) 440 ± 12 392 ± 10
Metals 2018, 8, x FOR PEER REVIEW 10 of 12
Elongation (%) 10.2 ± 0.1 9.9 ± 0.1
Ultimate tensile strength (MPa) 515 ± 15 485 ± 14
II
0.2%
0.2%yield
yield strength (MPa)
strength (MPa) 465
465 ±± 1111 429429±±9 9
Elongation
Elongation (%)(%) 9.9± ±0.20.2
9.9 9.49.4±±0.1
0.1
Ultimate
Ultimatetensile strength
tensile strength (MPa)
(MPa) 503
503 ±±1414 470470±±1212
III
III 0.2%yield
0.2% yield strength
strength (MPa)
(MPa) 453
453±±1010 405405±±9 9
Elongation (%) 10.0 ± 0.1 9.5 ± 0.1
Elongation (%) 10.0 ± 0.1 9.5 ± 0.1

SEM images
SEM images of of the
the tensile
tensile fracture
fracture in
in sample
sample II II along
along both
both thethe Y and Z
Y and Z direction
direction are
are presented
presented
in
in Figure 9. The presence of cracks was observed in both directions; however, the size of
Figure 9. The presence of cracks was observed in both directions; however, the size of the
the cracks
cracks
differed.
differed. TheThesize
sizeofofthe crack
the crackin the Y direction
in the was was
Y direction largerlarger
than that
thaninthat Z direction
the in and the and
the Z direction numberthe
of cracks in the Y direction was smaller. The presence of cracks is related to
number of cracks in the Y direction was smaller. The presence of cracks is related to the presence ofthe presence of brittle
metal
brittle compounds
metal compounds [17] and it indicates
[17] that thethat
and it indicates expansion of cracksofduring
the expansion cracks the deposition
during process
the deposition
mainly
processoccurs
mainlyalong
occurs Y direction.
thealong The Y direction
the Y direction. fracture was
The Y direction mainly
fracture wasplastic
mainlyfracture,
plasticas indicated
fracture, as
by dimples in Figure 9a. However, the fracture in the Z
indicated by the numerous dimples in Figure 9a. However, the fracture in the Z direction wasplastic
the numerous direction was not a single not a
or brittle
single fracture,
plastic but thefracture,
or brittle combination but of
thetwo fracture modes.
combination of two In Figure
fracture9b,modes.
both dimples and fractures
In Figure 9b, both
with lamellar stream patterns are observed. This phenomenon indicates
dimples and fractures with lamellar stream patterns are observed. This phenomenon indicates that that the fusing direction
greatly
the fusingaffects the plasticity;
direction however,
greatly affects the further investigation
plasticity; is needed
however, further to reduce the
investigation brittleness
is needed in the
to reduce
Z
thedirection.
brittlenessForinsamples I and III,For
the Z direction. thesamples
fractureImorphology is similar
and III, the fracture to sample II,
morphology is which
similarwill not be
to sample
repeated here.
II, which will not be repeated here.

Figure 9. Scanning electron microscopy (SEM) images of the tensile fracture in the (a) Y and (b) Z
Figure 9. Scanning electron microscopy (SEM) images of the tensile fracture in the (a) Y and (b)
direction.
Z direction.

4. Conclusions
4. Conclusions
This study demonstrates the feasibility of manufacturing 304 stainless steel/AA 4043 using
WAAM.ThisThe
study
maindemonstrates
experimentalthe feasibilityare
conclusions of as
manufacturing
follows: 304 stainless steel/AA 4043 using
WAAM. The main experimental conclusions are as follows:
(1) Columnar grains begin to grow from the area near the fusion line and transforms into equiaxed
(1) grains
Columnar grains
at the top ofbegin to growwall,
the buildup from and
the area near the
the grain sizefusion line with
decreases and transforms
increasing into equiaxed
travel speed.
grains at the top of the buildup wall, and the grain size decreases with increasing
(2) The specimen deposited using pulse current shows the better resistance to electrochemical travel speed.
(2) corrosion.
The specimen deposited using pulse current shows the better resistance to
electrochemical
(3) The hardness of corrosion.
the cladding layer is significantly greater than that of the base metal, which is
(3) related
The hardness of the cladding
to the formation layer is significantly
of intermetallic compounds, greater
such asthan that
Al1.1 Ni0.9of
. the base metal, which is
related
(4) This to the formation
manufacturing of intermetallic
method has little compounds,
effect on thesuch as Al1.1
tensile Ni0.9 . of the material. The
strength
elongation in the Y direction and Z direction reach 10.25% and 9.94%, respectively.
(5) The best parameters for fabricating SUS 304/AA 4043 alloy with WAAM are constant current of
150 A and scanning speed of 0.3 m/min.
Author Contributions: Conceptualization, Sansan Ao and Zhen Luo; Methodology, Zhizhuang Hao;
Writing-Original Draft Preparation, Zhizhuang Hao.; Writing-Review & Editing, Yangchuan Cai and Wei
Metals 2018, 8, 595 11 of 12

(4) This manufacturing method has little effect on the tensile strength of the material. The elongation
in the Y direction and Z direction reach 10.25% and 9.94%, respectively.
(5) The best parameters for fabricating SUS 304/AA 4043 alloy with WAAM are constant current of
150 A and scanning speed of 0.3 m/min.

Author Contributions: Conceptualization, S.A. and Z.L.; Methodology, Z.H.; Writing-Original Draft Preparation,
Z.H.; Writing-Review & Editing, Y.C. and W.Z.
Funding: This research was funded by the Natural Science Foundation of China grant number [51575383] and
Natural Science Foundation of Tianjin, China [18JCQNJC04100].
Acknowledgments: Thanks to the supports of experimental equipment from the School of Materials Science and
Engineering, Tianjin University.
Conflicts of Interest: The authors declare no conflict of interest.

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