Journal of Alloys and Compounds 840 (2020) 155753

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Understanding internal defects in Mo fabricated by wire arc additive

manufacturing through 3D computed tomography
Jiachen Wang a, Yinan Cui b, Changmeng Liu c, *, Zixiang Li c, Qianru Wu c,
Daining Fang a, d, **
a
Institute of Advanced Structure Technology, Beijing Institute of Technology, Beijing, 100081, China
b
Applied Mechanics Lab., Dept. of Engineering Mechanics, School of Aerospace, Tsinghua University, Beijing, 100084, China
c
School of Mechanical Engineering, Beijing Institute of Technology, Beijing, 100081, China
d
College of Engineering, Peking University, Beijing, 100871, China

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

Article history: Molybdenum (Mo) is an important high-temperature structural material but has poor processability.
Received 11 January 2020 Additive manufacturing (AM) leads to a new possibility of fabricating Mo structural parts. However, a
Received in revised form large number of internal defects appear during welding and AM processes in Mo and its alloys, which is
17 April 2020
far from well understood and has greatly limited their application. In this paper, the formation and
Accepted 20 May 2020
evolution mechanisms of internal defects in Mo are systematically studied, based on the state-of-the-art
Available online 23 May 2020
high-resolution computed tomography. This study demonstrates three main types of defects in Mo: (1)
small spherical pores; (2) inverted pear-shaped pores; and (3) cavities. The first type is similar to the
Keywords:
Wire arc additive manufacturing
observation in welded Mo, while the last two types are not reported before, which are associated with
Mo the heat cycling process during AM. The formation mechanism of different types of internal defects is
Defects proposed based on the experimental observations. The amount and morphology of internal defects are
Computed tomography quantitively and statistically discussed to understand the effect of fabrication parameters, which are
further explained according to their formation mechanisms.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction
Due to its high melting point, excellent mechanical properties
and low neutron absorption surface, molybdenum (Mo) and its
alloys play an important role in the aerospace [1,2], nuclear [3e6],
and electronics industries [7]. However, the high melting point and
high hardness make Mo and its alloys exhibit poor processability.
As a near-net-shape technique, additive manufacturing (AM)
has provided a new way to fabricate materials with poor process-
ability. This raises the possibility of fabricating complicated Mo
structures. However, till now, the primary focus of AM has been on
materials that are widely used and easy to fabricate, such as tita-
nium alloys [8e11], aluminum alloys [12e14], magnesium alloys
* Corresponding author. School of Mechanical Engineering, Beijing Institute of
Technology, Beijing, 100081, China.
** Corresponding author. Institute of Advanced Structure Technology, Beijing
Institute of Technology, Beijing, 100081, China.
E-mail addresses: liuchangmeng@bit.edu.cn (C. Liu), fangdn@pku.edu.cn
(D. Fang).
[15,16], and stainless steel [17e20]. Only a few studies are carried
out on refractory metals [21e24], especially Mo and its alloys
[25,26]. The internal defects are widely observed in welded Mo.
Since the last century, great efforts have been undertaken to un-
derstand them and try to eliminate them [27e38]. Therefore, it is
reasonable to expect that a large number of defects will be gener-
ated in Mo and its alloy fabricated by AM. This will significantly
degrade the performance of the materials.
Stütz et al. [35] used electron beam welding (EBW) to weld
TitaniumeZirconiumeMolybdenum (TZM) alloy plates. They found
that the optimal welding parameters were low input energy and
high welding speed. They also found that small grain size, small
heat-affected zone, and low porosity led to excellent mechanical
properties can be obtained at the same time. Xu et al. [31] used
electric resistance welding (ERW) to weld a 50Mo-50Re alloy. Pores
were also found inside the nugget, at the edge of the nugget, and in
the center of the welding zone. The positions of the pores were
irregular, so they suspected that the pores were caused by the in-
ternal defects from the powder metallurgy process. It was also
proposed that the powder metallurgy process plays an important

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2 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753
role, and it was necessary to improve the quality of it [33,39]. Some
researchers used energy-dispersive spectrometer (EDS) to analyze
the chemical compositions of the defect surface, based on the
consideration that defects are caused by impurities or oxidation
[32,37,38]. This suggests that the quality of raw materials should be
improved and cleaned before experiment, and provide shield gas to
avoid oxidation or other chemical reactions with low melting point
impurities during the manufacturing process. Impurities are likely
to cause cracks or pores at the grain boundary, so some researchers
use the addition of other alloy elements that are easy to combine
with oxygen to generate oxides to avoid the formation of molyb-
denum oxides to improve the strength at the grain boundary and
reduce pores [29,30,33].
Even though different researchers proposed different origins of
the internal defects, these studies suggest that the origin of the
defects in Mo and its alloys is mainly associated with Hydrogen (H),
Oxygen (O), low melting point compounds, powder metallurgy
defects, and processing parameters. These previous findings of the
welded Mo provide inspiration for understating the defects in Mo
by AM. Reducing the number of pores may be possible through
tuning the Mo composition [27,34,36] and the fabrication param-
eters [28,33].
However, the questions of controlling defects in Mo by AM are
still open. AM is associated with a more complicated heat cycling
process compared with the welding process. There may be some
unique types of defects as a result of AM. Systematic studies are
highly required in order to guide the AM process of Mo. Wire arc
additive manufacturing (WAAM) using arc as heat source and wire
as consumable has been rapidly developed in recent years [40e42].
Compared with the laser AM and electron beam AM, WAAM is
mainly applicated in the fabrication of large structural components
because of its higher deposition rate and low cost. Therefore,
disclosing the method of eliminating internal defects of Mo
through WAAM will lead to a new possibility of fabricating large
and complicated Mo structures.
Based on these considerations, this work is aimed at disclosing
the features and origins of internal defects formed in Mo during
WAAM. 11 molybdenum rods with columnar shape were fabricated
by WAAM. Different processing parameters were adopted to study
the evolution of the defects, and the internal defects were observed
and analyzed through the state-of-the-art high-resolution
computed tomography (CT). According to the result of the CT, the
amount and morphology of the defects are statistically analyzed
using three quantitative quantities. The formation mechanisms of
different types of internal defects are proposed based on the
experimental observations. These mechanisms are further used to
understand the effect of fabrication parameters on the formation
and feature of the internal defects. These shed light on under-
standing and eliminating defects in Mo during AM.
2. Experimental methods
2.1. The wire arc additive manufacturing experiments
The WAAM equipment was designed by the Beijing Institute of
Technology (Fig. 1). It was mainly composed of a computer nu-
merical control (Sinunerik 828D of SIEMENS), a machine unit, a gas
tungsten arc welding (GTAW) machine (Dynasty 700 of Miller),
wire feeder control (Series 9700 of Jetline), and an argon protection
unit that used 99.999% pure argon. The fabrication was done with a
welding torch, which was mainly composed of a tungsten electrode
that produces an arc and a wire feeder. In order to avoid oxidation,
the entire experiment chamber is protected by 99.999% argon at-
mosphere. In addition, the shield argon gas is continuously injected
to the local fabrication region with a flow rate of 20 L/min to further
protect the molten pool. The specific fabrication process involved
the tungsten arc continuously melting the wire and depositing
molten metal stacks in a layer-by-layer fashion.
Two groups of WAAM variable parameters for fabricating Mo
rods are shown in Table 1. One group has a constant base current of
60 A and 7 different peak currents of 200 A, 250 A, 300 A, 350 A,
400 A, 450 A, and 500 A. The other group has a constant peak
current of 300 A and 5 different base currents ranging from 40 A to
80 A. Table 2 shows the other constant parameters used in the
experiments. Due to Mo has high melting point, in order to keep a
stable process, the pulsed arc is used. In this way, instability due to
molten pool flow will be reduced. A pulsed arc of 10 s for a cycle was
used (Fig. 2(a)), and Fig. 2(b), (c) and (d) are the schematics of the
phenomenon in the manufacturing process. The pulse takes the
form of a square wave (Fig. 2(a)). The base current lasted for 9.5 s,
which was mainly used to melt the wire and form a droplet. The
peak current lasted for 0.5 s, which was mainly used to cover the
previous layer with a new droplet to produce a stable structure. The
substrates and wire were wiped with absolute ethanol to remove
oil and water before experiments. The diameter of the wire was
1.2 mm. Following these procedures, 11 Mo rods were successfully
fabricated (Fig. 3). Because the parameters used by Peak 3 and Base
3 are the same, we only fabricated 1 rod by this parameter. The
chemical compositions of the raw material are shown in Table 3.
2.2. CT testing
To analyze the morphology and distribution of the internal de-
fects in the Mo rods, CT testing was used to scan the samples. A
nano Voxel 4000 high-power micro-CT system was used (China
Tianjin Sanying Precision Instrument Co., Ltd.). In order to save time
and cost, we only scanned the rods of Peak 1, 3, 5, 7 and Base 1, 5.
Considering that it is very difficult to have high precision and large
scanned size at the same time, only 50 mm length from the bottom
of the samples was scanned. The testing parameters are listed in
Table 4. The final results were reconstructed using Avizo software.
In the end, quantitative data about the internal defects were
analyzed.
3. Results and discussion
3.1. Current dependent macroscopic morphology
From Fig. 3, it can be observed that the Mo rods were smoothly
fabricated. The main differences in the geometry of Mo rods reside
in the diameter when using different fabrication parameters as
listed in Table 1. We use the average diameter (f) to quantitatively
characterize them, because the cross-section of the rod is not
completely circular, and the surface of the rod is not perfectly
uniform. As the peak or base current increases, f gradually in-
creases from approximately 9 mm to approximately 12 mm, as
shown in Fig. 3(a)e(b). At the same time, the currents (I) and f
show an approximately linear relationship. Through fitting the
experimental data in Fig. 3(a) and (b), we find the following linear
dependence of f on the peak current (IP ) and base current (IB ),
f ¼ 0:01IP þ 7:1; f or IB ¼ 60A R2 ¼ 0:90029
(1)
f ¼ 0:059IB þ 6:37; for Ip ¼ 300A R2 ¼ 0:97994
Here, the unit of f is mm, and the unit of the current is ampere. Eq.
(1) demonstrates that the effect of IB on influencing the diameter is
more significant, compared with that of IP . R2 is the correlation
coefficient.
Such proportionality relation is explained as follows. As the
current continues to increase, the heat input from the arc also
 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753 3

Fig. 1. (a) Schematic of WAAM system [54]. (b) Overview of WAAM equipment [55].

Table 1
The two groups of WAAM variable parameters.

Group Sample ID Peak Current (A) Base Current (A)

Group 1 Peak 1 200 60

Peak 2 250 60
Peak 3 300 60
Peak 4 350 60
Peak 5 400 60
Peak 6 450 60
Peak 7 500 60

Group2 Base 1 300 40

Base 2 300 50
Base 3 300 60
Base 4 300 70
Base 5 300 80

Table 2
Constant parameters used in the experiment.

Processing parameter Value

Wire feeding speed 10 cm/min

Peak time ratio 5%
Pulse frequency 0.1 Hz
Shielding gas flow rate 20 L/min
Diameter of the electrode 3.2 mm
Angle between tungsten electrode and wire q 45
Diameter of the nozzle size 14 mm
Distance from the nozzle to the sample 4.5 mm
increases. At the same wire feed speed, the heat received by Mo
wire of the same quality also increases, so the temperature of the
droplets after the melting of the Mo wire is higher. The higher the
temperature is, the lower the surface tension [43] and the easier it
is for the droplet to spread and form a droplet with a large diam-
eter. Moreover, the variables in Fig. 3(a)e(b) increase linearly, thus
the temperature of the Mo rod increases linearly. As a result, the
surface tension decreases [43], resulting in the linear change of the
sample diameter.
3.2. Statistical analysis of the internal defects
The CT reconstructed results raise the possibility of analyzing
the 3D information of the internal defects. We carefully checked the
defects in each sample, and two representative samples are chosen
and shown here for Peak 1 (Fig. 4) and Peak 7 (Fig. 5) from Group 1
in Table 1. It can be seen that both large and small defects with
complicated shapes appear inside the samples, as shown in
Figs. 4(c) and 5(c).
Fig. 2. (a) Schematic of the pulsed arc fabrication process. For each pulse, a small
current (base current, blue shaded area) and a large current (peak current, red area)
occurred at different times. (b) and (c) schematically show that in the base current
stage, the wire is melted and a droplet is formed. (d) schematically shows that in the
peak current stage, the previous layer is covered by the droplet. The angle between
tungsten electrode and wire is q. The wire feeding speed is f, and during the peak
current time, the torch moves with speed v. (For interpretation of the references to
colour in this figure legend, the reader is referred to the Web version of this article.)
To further analyze these defects, we classify these defects ac-
cording to their shapes and sizes. We introduce a critical pixel
volume Vc , which is set to 30000 pixels (about 0.03 mm3). If the
volume of the defect Vd is smaller than Vc , it is recognized as a small
spherical pore (SSP), otherwise, it is defined as a large pore. Similar
small spherical pores are also widely observed during the welding
of Mo as discussed in the introduction [44].
The uniqueness of the internal defects for additive manufac-
tured Mo is the large pore with a special shape. To the best of our
knowledge, such phenomena are never reported. This is expected
to be related with the heat cycling effect during AM and will be
discussed further in section 3.3. For better visualization, we
removed the SSPs in Figs. 4(d) and Fig. 5(d)., so that only large pores
4 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753

can be observed. In Fig. 4(d), there are some special shape defects
(Fig. 4(e)), and we defined them inverted pear-shaped pore (IPP). In
Fig. 5(d), there are some defects with complicated shapes in the
center of the whole rod (Fig. 5(e)), and we called them cavity.
In order to further quantitatively obtain the relationship be-
tween the current and the internal defects, we defined the
following physical quantities.

(1) Dense degree D, which is defined as the ratio of the volume

of the solid matter to the total volume.

D ¼ ðV0 = VÞ  100% (2)

where V0 is the volume of the solid, V is the total volume of the rod.

(2) Defect volume Vd , which is the volume of a specific defect

and reflects its size.
(3) Sphericity S, which is defined as the ratio of the surface area
of the sphere of the same volume to the surface area of the
defect.
qffiffiffiffiffiffiffi
4p 2 3V
3
d
4p
S¼ (3)
Ad

where Vd is the volume of the defect, Ad is the surface area of the

defect.
The first quantity reflects the amount of the internal defects,
while the second and the third quantities reflect the morphology of
the internal defects. In the following, all these physical quantities
will be analyzed one by one, to quantitatively describe the internal
defects.

3.2.1. Amount of internal defects

The amount of internal defects is described by the dense degree
D. It can be seen that if IB is constant, as IP increases, D increases
(Fig. 6(a)). They follow the following linear relations,

D ¼ 0:032IP þ 81:474 (4)

However, with IB increasing, D is not sensitive to IB , as shown in

Fig. 6(b). Such dependence on IP and IB will be explained in detail in
section 3.3.3.

Fig. 3. (a) The relationship between the average diameters of rods and peak current in
3.2.2. Morphology of internal defects
Group 1. (b) The relationship between the average diameter of rods and base current in
Group 2. The diameter of the samples shown in the figure is numerically labeled.
The morphology of the defects is characterized through the
distribution of the defect volume and the sphericity. According to
the results of the experiments, there are a large number of SSPs in
Table 3 the rod. Fig. 7 shows the number fraction of defects with different
Chemical compositions of the raw materials used in the experiments (wt%). sizes in the rods. The number of SSPs is far more than the large
Mo Fe Ni Si C N O pores. We calculated the total volume of SSPs, which is less than
20 mm3. Therefore, even though their number is much larger, their
Balance 0.0052 <0.001 <0.001 0.032 0.0026 0.17
contribution to the dense degree D is smaller. Note that the for-
mation of SSPs is important for the formation of other, which will
be explained further in Section 3.3.
Table 4
The parameters used for CT testing. Here, SOD is the
The statistical distributions of sphericity S of the internal defects
source to object distance, and SDD is the source to de- are shown in Fig. 8. Since the number fraction of the SSP and larger
tector distance. pores are significantly different (Fig. 7), it makes more sense to
Testing parameter Value
distinguish the distribution of the sphericity of SSPs and larger
pores. It can be seen from Fig. 8 that the averaged sphericity of SSPs
SOD (mm) 52.00
is larger than the large pores. For large pore, the possibility of
SDD (mm) 640.74
Exposure time (s) 0.60 observing spherical pore is very low. This can also be observed in
Voltage (kV) 200.0 Figs. 4 and 5.
Current (mA) 100.0 In order to further reveal the correlation between the defect size
Resolution (mm) 0.010 and its sphericity, we present the corresponding data for each
defect in Fig. 9. It can be observed that most of the small defects are
 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753 5

Fig. 4. (a) Peak 1 sample fabricated with IP ¼ 200A and IB ¼ 60A. (b) An original scan tomogram of the red area in (a). (c) The reconstructed image of the blue area in (b). For better
visualization, (d) is the image of (c) without the SSPs. (e) The image of the yellow area in (d). (For interpretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)

Fig. 5. (a) Peak 7 sample fabricated with IP ¼ 500A and IB ¼ 60A. (b) An original scan tomogram of the red area in (a). (c) The reconstructed image of the red blue in (b). For better
visualization, (d) is the image of (c) without the SSPs. (e) The image of the red yellow in (d). (For interpretation of the references to colour in this figure legend, the reader is referred
to the Web version of this article.)
6 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753
Fig. 6. (a) The relationship between the dense degree of rods and peak current. (b) The relationship between the dense degree of rods and base current. (a) shows a linear
relationship, and (b) shows an invariant relationship.
Fig. 7. The number fraction of the defect volume of sample Peak 1 and sample Peak 7.
near-spherical, but large defects have relative low sphericity for all
the considered fabrication currents. This trend is also shown in
Figs. 4 and 5. The SSPs are observed, and the large defects exhibit
inversed-pear shape or irregular shape.
Fig. 8. The probability of S in two different samples. Here, S is sphericity.
3.3. Formation mechanism of the internal defects
Based on the observation of the dependence of the internal
defects on the current, we proposed the following formation
mechanism of the internal defects.
3.3.1. Features and formation mechanism of small spherical pores
(SSP)
As described in section 3.2, in the current work, SSP is defined as
the internal defect, whose volume is less than 0.03 mm3, so its
equivalent diameter is 0.19 mm. As shown in section 3.2.2, its S is
relatively high. The number fraction of SSP is also much higher,
compared with large internal defects.
Based on these information, the formation and evolution pro-
cess of SSP will be described as follows. When the metal is melted
to form a molten pool, a large number of SSPs appeared inside, as
shown in Fig. 10(a). Due to the influence of surface tension and arc
flow, the flow of liquid metal is schematically marked using the
arrows in Fig. 10(b) [45,46]. Because of the molten pool flow, SSPs
move accordingly [47]. Because the volume of the SSP is small, the
buoyancy force Fb had little influence on the SSPs. Therefore, they
do not escape due to the buoyancy force (Fb ). There are two other
forces acting on them: one is the drag force (Fd ) induced by melt
flow, the other is the thermocapillary force (Ft ) induced by tem-
perature gradient around the pore [48]. SSPs are driven by Fd and Ft
to rotate in the molten pool (Fb ≪Fd , and Fb ≪Ft ). Therefore, they
will continue to exist in the molten pool [48]. This explains why the
number fraction of SSP is very high. A similar process also occurs
 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753 7

Fig. 9. The relationship between defect volume Vd and the sphericity S in two different samples.

Fig. 10. Schematic showing the formation of the IPP. (a) The formation of the SSPs. Because of the liquid agitation in (b), the SSPs coalesce to form large pores in (c). (d) Some region
is remelted when the next layer is deposited on top. Because the bottom of large pore is below the remelted line in (e), its size does not grow, and the size in the top region will grow
continuously to form IPPs in (f). When the IPPs are large enough, some parts of the pores escape due to the Fb , and the IPPs are left below the remelted region in (g).

during welding, so SSPs are also observed during welding. During
WAAM, after the molten pool solidifies, the deeper region will not
be remelted even when the subsequent layer is deposited, so the
SSPs remain in the sample.
3.3.2. Features and formation mechanism of inverted pear-shaped
pores (IPP)
The morphology of IPP is given at higher magnification in
Fig. 4(e) for better visualization. Here, inversed pear-shaped means
that the size of the bottom region of the pore is smaller than that of
the upper region. Such kind of large IPPs are not reported during
welding, so they are expected to be related to the special heat
cycling process during AM. This supposition is also supported by
our experiments. Firstly, the wire does not contain large defects.
Secondly, the rod is formed layer by layer. The thickness of each
layer fabricated by each parameter in Table 1 is not larger than
0.5 mm. However, the longitudinal length of IPPs mostly exceeds
0.5 mm, so IPP cannot be formed by one layer. They must be formed
due to the gathering of SSPs and growth.
Based on these considerations, their formation mechanism is
analyzed as schematically shown in Fig. 10. As mentioned in Section
3.3.1, the SSPs will rotate in the molten pool. This leads to the
possibility that they will absorb each other and gradually gather to
become larger, as shown in Fig. 10(c). Moreover, The flow velocity in
the molten pool can reach 100 m/s [49]. Even within 0.5 s, the
moving distance of the pore is long. That accelerates the occurrence
of these reactions. During the process of solidification, some of the
pores are left in the top region of the sample. When the next layer is
deposited, the droplet accumulates on top of the previous stacking
position, as marked by the dotted line in Fig. 10(d). There is a
remelted region. The remelted area is above the yellow line in
Fig. 10(d) and is composed of molten metal. The SSPs in the
remelted region will have the chance to be absorbed by the large
pores or gathered again (Fig. 10(d)). This phenomenon is repeated
throughout the experiment, and the pores increase in size. Until
then, the large pores remain spherical due to the surface tension
force. When the pores are large enough, the depth of the remelted
region cannot reach the bottom of the pores (Fig. 10(e)). The bottom
is not melted, and its shape remains. Meanwhile, the pores in the
upper region still absorb the SSPs and grow. In addition, because
8 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753
Fig. 11. Schematic for the formation of cavities in the center. (a) The keyhole due to the peak current arc. The steam in the keyhole is covered by the backfilling molten pool in (b) to
form a cavity in (c). When the next peak current arc forms, steam invades the cavity to increase the size of the cavity in (d). As the experiment progresses, the cavity continues to
grow in (e). Eventually, an elongated cavity with an irregular surface in (f) is formed. Then, the next peak current will not affect the cavity in (f), just show in (g).
the temperature in the upper region is higher than that in the lower
region, more significant gas expansion occurs in the upper region.
The gas-molten metal interface at the top side of the pore moves
under the action of expansion pressure, while the gas-solid metal
interface at the bottom side of the pore is much less influenced.
Therefore, larger diameter is observed in the upper region,
contributing to the formation of IPP. Soon after, an IPP is formed
(Fig. 10(f)). Then, the IPPs absorb other SSPs and expand to a certain
extent, and the pores become very large, which increases the Fb .
Meanwhile, the Fb dominates the process, and some of the gas at
the top escapes. This volume of escaped gas is backfilled rapidly by
molten metal and solidified (Fig. 10(g)). When the next droplet
came, the depth of the remelted region cannot reach the top of the
IPP. Thus, an IPP is left. At this time, the upper region cannot
continue to grow up.
According to the experimental observation from Fig. 4, the up-
per region of IPPs can have width larger than the depth of the
molten pool, but the top surface of the IPP is curved, instead of very
flat. This can be explained as follows. Firstly, if a pore exhibits
hemispherical shape on the upper region, one possible extreme
case is that the radius of the hemispherical part is close to the depth
of the molten pool d. For this case, the width of the hemispherical
part is close to 2d. Therefore, when d is close to 2 mm (triple depth
of the molten pool), it is possible to observe pores with width larger
than 2 mm. As can be seen from Fig. 4, the upper region of IPPs are
almost 4 mm. According to the 2 mm depth of the molten pool, the
extreme case is that the upper region shows a hemisphere, so the
top surface will not be flat. Secondly, the escape of the gas from the
upper region of IPPs can change its final shape. As the upper region
of IPP continues to increase, the buoyancy of the upper region also
continues to increase. This mechanism successfully explains the
special inversed pear-shape and their larger size compared with
SSP.
3.3.3. Features and formation mechanism of cavities
The cavities refer to the large pore with an irregular shape, as
clearly shown in Fig. 5(e). To the best of our knowledge, such huge
cavities with volume about 30 mm3 are never reported. This is
because the additive manufacture studies on Mo are very limited,
and the 3D CT reconstructed results of additive manufactured Mo is
even rarer. In addition to their large size and irregular shape, the
cavities exhibit two other features. One is that they are positioned
in the center of the rod. The other is that they are only observed
when the peak current is higher than a critical value (450 A) with
our parameters.
Based on these information, we proposed that the cavity origi-
nates at the keyhole (Fig. 11(a)), which is similar to the behavior of
keyhole during laser processing [28,50]. Similarly, the K-TIG uses
keyhole to improve welding results, so the arc can form a keyhole
when the current is high enough [51].
It is well known that the principle of arc welding is to ionize the
gas to plasma to generate energy. The plasma is subjected to an
electromagnetic force throughout the arc region. It caused the
plasma to move to the anode (molten pool) fast [52]. At relatively
small currents, high speed of deposition can be generated, causing
the molten pool to sag. Therefore, the higher current corresponds to
more significant compression [53], which is schematically shown in
Fig. 11(a). This phenomenon is also observed during the
experiment.
The high energy in the keyhole causes the metal to be melt to
vaporize. A steam pore is generated in the lower part of the center
of the molten pool (Fig. 11(b)). The vapor in the steam pore has not
yet liquefied or escaped, and the upper molten metal backfills and
solidifies rapidly, so there is a steam pore (Fig. 11(c)). The temper-
ature decreases before the subsequent peak current is generated.
Therefore, the steam pore is liquefied and solidified. There is little
gas inside the defect, so it is called a cavity rather than a pore. When
the next peak current is generated, the upper part of the cavity is
opened, and metal vapor invades into the cavity (Fig. 11(d)). At this
time, the pressure of the steam (ps ) is larger than the pressure of
the upper molten metal (pl ), namely ps > pl. Therefore, the upper
molten metal will not enter the steam pore. This phenomenon is
repeated throughout the experiment, and a relatively long cavity is
formed (Fig. 11(e)).
Since the peak current vaporizes molten metal with a certain
quality, the amount of the metal steam that fills the cavity also has a
specific value (mv ). The volume of the cavity (Vcav ) enlarges
continuously, but the quality of the metal vapor entering the cavity
is still mv . According to the ideal gas law:
ps Vcav ¼ nRT (5)
where mv is a fixed value, so n is fixed, too. Therefore, when Vcav
becomes larger, ps becomes smaller. Because pl is a fixed value,
 J. Wang et al. / Journal of Alloys and Compounds 840 (2020) 155753
when Vcav increases to a certain extent, so ps < pl . Then, the upper
molten metal will enter the steam pore, and Vcav is reduced, so ps
increased again. While ps ¼ pl , the upper molten metal will not
enter the steam pore again, then, it solidified outside the pore
(Fig. 11(f)). When the next peak current is generated, the top of the
cavity is not affected by the arc, so there is no metal steam to
enlarge the cavity, and the new metal steam leads to the formation
of another cavity (Fig. 11(g)). The surface of these cavities is very
irregular due to the absorption of other SSPs at the edges.
3.4. More insights based on the formation mechanism
In section 3.3, the formation mechanisms of different internal
defects are proposed, which clearly explain their shape features. In
the following, their formation mechanism will be used to further
understand their statistical observations presented in section 3.2.
3.4.1. Current dependent dense degree
According to section 3.3, it is difficult for the SSPs to escape by
Fb , but it is easier for the large pores to escape. Since the other
parameters do not change as IP increases, the layer height (thick-
ness of the droplet deposition) decreases, and the remelted depth
increases in size, so there are more regions, where SSPs have the
opportunity to be gathered. As a result, more large pores are pro-
duced, which also generates an increased Fb , so there is a sub-
stantial amount of gas to escape. Therefore, higher D is observed for
higher IP as shown in Fig. 6(a).
The effect of IB is different. As the IB increases, the solidification
time increases. As a consequence, the impurities in the material
react for an increased amount of time in the molten metal, which
produces more gas in the rod. Therefore, IP can effectively reduce
the existence of defects, but IB cannot.
3.4.2. Size dependent sphericity
According to section 3.3, SSPs are not sensitive to the heat
cycling process. Therefore, SSP has higher sphericity due to surface
tension effect. In the current work, the thickness of each deposition
layer in the rod does not exceed 0.5 mm. Considering the effect of
remelting, the depth of the molten pool will not exceed 2 mm, so
the diameter of the spherical defect will not exceed 2 mm in the
molten pool, and its volume Vd will not exceed 2.4 mm3. Therefore,
any pore that has a diameter of less than 2 mm can form a spherical
pore in the molten pool. The large IPP and cavities are strongly
associated with the layer by layer deposition process. Therefore,
they have a longer size along the deposition direction, as explained
in Figs. 9 and 10. These analyses explain the observation shown in
Fig. 8.
4. Conclusion
Fabricating Mo with complicated structure is very important but
also very challenging. AM provides a new pathway to achieve this
goal, but the related work is very limited. More efforts are signifi-
cantly required to understand how to control the internal defects
during AM. In this work, Mo rods were fabricated by WAAM.
Through state-of-the-art high-resolution computed tomography,
the 3D information of the internal defects in additive manufactured
Mo is for the first time quantitatively and statistically analyzed. Our
results show several intriguing findings.
(1) The defects in Mo by WAAM can be categorized as small
spherical pores (SSP), inverted pear-shaped pores (IPP), and
cavities. Among them, the SSPs are similar to the observa-
tions in welding Mo, but the large pores and cavities are not
reported before in welding Mo.
9
(2) The formation mechanism of different types of internal de-
fects is proposed based on the experimental observations.
SSPs cannot escape because of the insignificant buoyancy.
The IPPs in the Mo rod are formed by the collapse of SSPs,
which is related to the remelting process. The cavities are
formed by keyholes, which are caused by a high peak cur-
rent. If the peak current exceeds 450 A, Mo is vaporized to
form a keyhole.
(3) The dense degree is found to be linearly dependent on the
peak current, but is insensitive to the base current. The
sphericity of the pore is size dependent. The smaller the pore
size, the higher the sphericity. These observations are
explained through the formation mechanism of the internal
defects.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Jiachen Wang: Writing - original draft, Formal analysis, Inves-
tigation, Visualization. Yinan Cui: Writing - review & editing,
Methodology. Changmeng Liu: Conceptualization, Methodology,
Project administration. Zixiang Li: Writing - review & editing,
Visualization. Qianru Wu: Writing - review & editing. Daining
Fang: Supervision.
Acknowledgement
The work was financially supported by the National Natural
Science Foundation of China (51875041, 11972208, 51875042).
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