metals
Article
Effect of Hydrogen on the Tensile Behavior of Austenitic
Stainless Steels 316L Produced by Laser-Powder Bed Fusion
Farzaneh Khaleghifar 1 , Khashayar Razeghi 1 , Akbar Heidarzadeh 2, *






Citation: Khaleghifar, F.; Razeghi, K.;
Heidarzadeh, A.; Taherzadeh
Mousavian, R. Effect of Hydrogen on
the Tensile Behavior of Austenitic
Stainless Steels 316L Produced by
Laser-Powder Bed Fusion. Metals
2021, 11, 586. https://doi.org/
10.3390/met11040586
Academic Editor: Babak
Shalchi Amirkhiz
Received: 5 March 2021
Accepted: 31 March 2021
Published: 3 April 2021
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Copyright: © 2021 by the authors.
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This article is an open access article
distributed under the terms and
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Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Metals 2021, 11, 586. https://doi.org/10.3390/met11040586
and Reza Taherzadeh Mousavian 3
1 Razi Applied Science Foundation, P.O. Box, Tehran 37531-46137, Iran; khaleqifar.farzaneh@gmail.com (F.K.);
kh.razeghi@gmail.com (K.R.)
2 Department of Materials Engineering, Azarbaijan Shahid Madani University, P.O. Box, Tabriz 53714-161, Iran
3 I-Form, Advanced Manufacturing Research Centre & Advanced Processing Technology Research Centre,
School of Mechanical & Manufacturing Engineering, Dublin City University, 9 Dublin, Ireland;
rezataherzadeh.mousavian@i-form.ie
* Correspondence: ac.heydarzadeh@azaruniv.ac.ir
Abstract: Hydrogen was doped in austenitic stainless steel (ASS) 316L tensile samples produced
by the laser-powder bed fusion (L-PBF) technique. For this aim, an electrochemical method was
conducted under a high current density of 100 mA/cm2 for three days to examine its sustainability
under extreme hydrogen environments at ambient temperatures. The chemical composition of the
starting powders contained a high amount of Ni, approximately 12.9 wt.%, as a strong austenite
stabilizer. The tensile tests disclosed that hydrogen charging caused a minor reduction in the elonga-
tion to failure (approximately 3.5% on average) and ultimate tensile strength (UTS; approximately
2.1% on average) of the samples, using a low strain rate of 1.2 × 10−4 s−1 . It was also found that an
increase in the strain rate from 1.2 × 10−4 s−1 to 4.8 × 10−4 s−1 led to a reduction of approximately
3.6% on average for the elongation to failure and 1.7% on average for UTS in the pre-charged samples.
No trace of martensite was detected in the X-ray diffraction (XRD) analysis of the fractured samples
thanks to the high Ni content, which caused a minor reduction in UTS × uniform elongation (UE)
(GPa%) after the H charging. Considerable surface tearing was observed for the pre-charged sample
after the tensile deformation. Additionally, some cracks were observed to be independent of the melt
pool boundaries, indicating that such boundaries cannot necessarily act as a suitable area for the
crack propagation.
Keywords: laser powder bed fusion (L-PBF); hydrogen embrittlement (HE); austenitic stainless steels
(ASSs); tensile properties
1. Introduction
Additive manufacturing processes selectively add materials layer-by-layer to build
3D models. Among the most popular processes for the additive manufacturing of metals
is laser-powder bed fusion (L-PBF) [1]. During this process, a high-energy laser beam
irradiates the powder layer, and energy is absorbed by powder particles through bulk-
coupling and powder-coupling, generating an extremely high temperature and a rapid
cooling rate within the molten pool [2].
Austenitic stainless steels (ASSs) can be used in a wide range of applications due
to their properties, such as a good combination of strength and ductility and corrosion
resistance [3]. The 316L grade is a type of ASS, which has attracted the attention of
engineers and researchers in both academic and industrial areas [4]. Numerous studies
have shown that L-PBF of 316L ASS results in a microstructure different from that of
traditional 316L ASS, which can cause improved mechanical responses [5,6]. The mentioned
unique properties of ASSs, including 316L ASS, have made them a promising material
for application in the hydrogen industry, especially in the production of gaseous or liquid
hydrogen storage used in transportation vehicles [7]. However, it is well understood that
https://www.mdpi.com/journal/metals
Metals 2021, 11, 586 2 of 12

the hydrogen embrittlement (HE) is a critical issue for this group of materials when used
in highly deformed conditions [8–14]. This has stimulated researchers to study the HE of
ASSs and to overcome the problem.
Recently, some researchers [15–17] have reported the response of laser-powder bed fu-
sioned (L-PBFed) 304L and 316L in mild and extreme hydrogen environments. Baek et al. [16]
reported the high resistance of L-PBFed 304L for hydrogen services, in which no phase trans-
formation from austenite to martensite was detected, despite a meta-stable microstructure
of 304L. They provided the tensile test results under the crosshead speed of 0.0012 mm/s,
which corresponds to an initial strain rate of 10−4 /s and a reduction in elongation from ap-
proximately 64 to 59% that occurred in a hydrogen atmosphere. However, a fracture surface
with small and uniform dimples was observed for their samples in both the air and hydro-
gen atmospheres, indicating no sign of HE. In another study, Lee et al. [17] systematically
investigated the hydrogen effects on the tensile ductility of 304L fabricated by L-PBF. The
hydrogen was charged for one and five days using current densities of 20 and 50 mA/cm2 ,
respectively. A slight effect on ductility was reported in their study, with a small amount
of α0 martensite (approximately 3 vol.%) at the strain level of 60%, suggesting that the
high local mechanical stability of austenite could be responsible for the HE resistance. In
addition, they found a negligible effect of the solidification cell structure (cellular structure
emanates from the Marangoni effect and elemental segregation during the rapid cooling
during the L-PBF process [18]) on austenite stability, as well as on H trapping behavior. It
was reported in their study that cellular structure may not provide additional H trapping
sites and thus a H content increment, while an increase in the dislocation density of the
L-PBFed sample could be more responsible as the trapping sites, and HE susceptibility
might not be increased by increasing the H content. Finally, they found that in the absence
of deformation-induced martensite in meta-stable stainless steels (SSs), a slow crack growth
can be expected during the tensile deformation. In another recent study, Park et al. [6]
studied the H uptake and its influence on L-PBFed ASS 316L using a low current density
of 5 mA/cm2 for 6 and 24 h nanoindentation measurement. They found that the cellular
structure of L-PBFed ASSs containing a high density of dislocations might not enhance the
H absorption capacity and H-induced mechanical degradation.
Based on these recent findings, it seems that L-PBFed ASSs may have suitable HE
resistance. However, the tensile behaviour of L-PBFed ASS 316L with a high Ni content
for the stabilization of the austenite phase in an extreme hydrogen environment is lacking.
In this study, ASS 316L powders that contain 12.9 wt.% Ni were used to examine the HE
resistance of L-PBFed ASSs under extreme hydrogen environments. Shibayama et al. [19]
reported that the crack growth rate under the hydrogen charging at a higher current density
was higher than that at a lower current density, which denoted that a higher hydrogen
fugacity promoted the faster growth of cracking. For this purpose, in this study, a high
current density, which may lead to a higher amount of hydrogen after charging [20], was
used for three days before the tensile test.

2. Materials and Methods

The gas-atomized Fe-Cr-Ni ASS pre-alloyed powder with a Gaussian size distribution
ranging from 15 to 50 µm was used in this work. A cylindrical bar with a height of 60 mm
and a diameter of 10 mm was vertically printed by an EOSINT M280 3D (EOS, Freiburg,
Germany) printing system, with a discontinuous Yb-fiber laser and maximum power
capacity of 200 W under argon atmosphere. The chemical composition of the L-PBFed bars
was determined by an optical emission spectrometer (Oxford Instruments—PMI-Master
Smart, UK). The combined parameter energy density (ED) is frequently used to evaluate
printing parameters. In the present work, the value of ED was determined to be 100 J/mm3 .
The chemical composition of the L-PBFed 316L alloy is listed in the upper part of Table 1.
Metals 2021, 11, 586 3 of 12

Table 1. Chemical compositions of bulk L-PBFed austenitic stainless steel (ASS) 316L in conjunction
with conditions of different experiments in this study.

Chemical Compositions
Material C Mn P S Cr Mo Ni Si Cu Fe
L-PBFed SS316L 0.025 0.76 0.009 0.010 17.30 2.30 12.90 0.642 0.026 Bal.
Condition of Experiments
Sample Strain Rate (S−1 )
Uncharged, UC-1.2 1.2 × 10−4
Charged, C-1.2 1.2 × 10−4
Charged, C-4.8 4.8 × 10−4

The L-PBF sample bars were machined to produce cylindrical dog-bone specimens
with a gauge length of 16 mm and a diameter of 4 ± 0.1 mm, according to the ASTM E8/16a
standard. Hydrogen was pre-charged into the tensile samples by the electrochemical
method (Figure 1). The samples were immersed in a distilled water solution containing
3 wt.% NaCl and 0.3 wt.% NH4 SCN. The efficiency of this solution in the H permeation
was reported several times in the literature [19,21–29]. Ammonium thiocyanate (NH4 SCN)
is widely used as a reagent (hydrogen recombination poison) for promoting hydrogen
absorption by steels, and during hydrogen charging, the solution was de-aerated with
N2 [22,30]. Samples were connected to a cathode, and a Pt coil was connected to the
anode. To ensure absorption of a high amount of hydrogen into the samples, a high current
density of 100 mA/cm2 was applied for three days at room temperature. Three tensile tests
per condition were performed at room temperature just 20 min after charging (to ensure
minimum outgassing) using a Universal Testing Machine (STM-20, Santaam, Tehran, Iran).
The lower part of Table 1 summarizes the used samples in this study with or without
Metals 2021, 11, x FOR PEER REVIEW the
4 of 13
hydrogen charging process tensile tested at two different strain rates.

Figure The
1. 1.
Figure electrochemical
The electrochemicalprocess
processfor
forhydrogen
hydrogen charging of L-PBFed
charging of L-PBFedsamples.
samples.

After the tensile test, the microstructures of the samples and fractured surfaces were
investigated using an optical microscope (OM) (3d imaging: OPTIKA B-383MET-Pon-
teranica, Italy) and an scanning electron microscope (SEM) (MIRA3 TESCAN, Czech Re-
Metals 2021, 11, 586 4 of 12

After the tensile test, the microstructures of the samples and fractured surfaces were in-
vestigated using an optical microscope (OM) (3d imaging: OPTIKA B-383MET-Ponteranica,
Italy) and an scanning electron microscope (SEM) (MIRA3 TESCAN, Czech Republic, SEM
HV: 15.0 kV, window Type: Moxtek AP1.3). For this aim, the samples were mechanically
ground with fine SiC papers (grit number up to 2000) and subsequently polished with
3 µm diamond suspension and finally with 0.05 µm silica suspension. Finally, to confirm
the austenite stability, XRD analysis was performed using an Explorer (GNR-Analytical
Instruments Group, Italy, CuKα, λ = 1.5406 Å, 40 kV, 30 mA, and step size 0.01).

3. Results
Figure 2 shows the microstructure of the L-PBFed 316L before the hydrogen charg-
ing. It is worth noting that the laser scanning direction was rotated by 67◦ after each
layer, leading to differently oriented melt pools, as depicted. Many grains include melt
pool boundaries (MPBs), suggesting the epitaxial growth of new grains from re-melted
zones [31]. The presence of MPBs and such epitaxial growth, which forms a texture, is
among the specific characteristics of the L-PBFed materials that can directly affect 5their
Metals 2021, 11, x FOR PEER REVIEW of 13
mechanical properties along different axes.

Figure 2. OM micrographs of as-built sample before hydrogen charging, produced by L-PBF. The
Figure 2. OM micrographs of as-built sample before hydrogen charging, produced by L-PBF. The
image is perpendicular to the building direction.
image is perpendicular to the building direction.

InFigure
In Figure3,3,the
thetensile
tensilecurves—in
curves—inconjunction
conjunctionwith
withtensile
tensileproperties,
properties,such
suchasastensile
tensile
yield strength (YS), ultimate tensile strength (UTS), and elongation (EL), of
yield strength (YS), ultimate tensile strength (UTS), and elongation (EL), of specimens—are specimens—
are illustrated,
illustrated, fromfrom
which which the following
the following resultsresults
can becan be extracted.
extracted. It isunderstood
It is well well understood
that
that L-PBF causes the formation of cell structures and a high density of dislocations,
L-PBF causes the formation of cell structures and a high density of dislocations, which which
resultsininthe
results thestrengthening
strengthening ofof ASSs
ASSs [32].
[32]. The
The charging
charging of hydrogen
of hydrogen caused
caused lower
lower values
values of
of elongation and strength, which means that the overall performance
elongation and strength, which means that the overall performance of these steels withof these steels with
a
a high
high NiNi content
content is suitable
is suitable after
after thethe intensive
intensive pre-charging
pre-charging of H.
of H.
Metals 2021, 11, 586 5 of 12
Metals 2021, 11, x FOR PEER REVIEW 6 of 13

Figure
Figure 3.
3. Engineering
Engineering stress–strain
stress–strain curves
curves ofof different
different samples,
samples, i.e.,
i.e., UC-1.2,
UC-1.2, C-1.2,
C-1.2, and
and C-4.8.
C-4.8. The
The tensile
tensile properties
properties and
and
images of fractured surfaces after tensile tests are superimposed below the tensile curves.
images of fractured surfaces after tensile tests are superimposed below the tensile curves.

Figure
Figure44 shows
shows the the cross-sectional
cross-sectional microstructures
microstructures of of fractured
fractured tensile
tensile samples.
samples. The The
following
following results from Figure 4 can be summarized as follows: (1) In the case of
results from Figure 4 can be summarized as follows: (1) In the case of samples
samples
without
without hydrogen
hydrogen charging
charging (Figure
(Figure 4a,b),
4a,b), there
there were
were some
some fine
fine cracks
cracks fromfrom which
which the the
fracture
fracturecould
couldbebeinitiated.
initiated.These
Thesefine
finecracks
cracksare aremarked
markedby bythe
thewhite
whitearrows
arrowsin inFigure
Figure4a. 4a.
(2)
(2)After
Afterhydrogen
hydrogencharging
charging (Figure
(Figure 4c–f),
4c–f), the
thecracks
crackswere
werelarger,
larger, as
as indicated
indicated by by the
the white
white
arrows
arrowsin inFigure
Figure4c,d.
4c,d.The
Thecracks
crackswere
were propagated
propagated along
alongthethe
MPBs
MPBs (dashed
(dashed white
whitelines in
lines
Figure 4e). No sign of MPB-induced cracking can be observed in Figure
in Figure 4e). No sign of MPB-induced cracking can be observed in Figure 4f, in contrast 4f, in contrast with
Figure 4b,e, 4b,e,
with Figure indicating that that
indicating MPBs do not
MPBs do not necessarily
necessarilyactact
asassuitable
suitablezoneszonesforfor crack
crack
propagation,
propagation,and andthere
there might
might be be multiple
multiple sources
sources of
of crack
crack initiation
initiation and
and propagation
propagation in in
H-charged
H-charged L-PBFed
L-PBFed SSs. SSs. Moreover,
Moreover,the the deformation
deformation mechanisms
mechanisms of of all
all samples
samples were were
controlled slipand
controlled by slip andtwinning,
twinning,due dueto to
thethe formation
formation of large
of large amounts
amounts of mechanical
of mechanical twins
twins
insideinside the grains.
the grains.
The SEM micrographs of tensile fractured surfaces in conjunction with energy-dis-
persive X-ray spectroscopy (EDS) analysis are shown in Figures 5 and 6. The fracture sur-
faces included both the cleavages and dimples as the characteristics of brittle and ductile
fracture modes, respectively. However, the ductile mode was the dominant fracture
mechanism. In addition, there were some porosities in the fracture surface of the L-PBF
samples (white arrow in Figure 5b). Moreover, the EDS analysis of points A and B in Fig-
ure 5b showed that in point A, beside the voids, a segregation of alloying elements oc-
curred. There was a similar trend in the case of points A and B in Figure 6 for C-4.8 sample.

Metals 2021, 11, 586
The segregation of elements in L-PBFed stainless steel 316L has been reported many times
[33,34]. A high solidification rate and lack of equal mobility of elements during solidifica-
tion are the main reasons for obtaining such elemental segregation that may cause 6 ofthe
12
formation of a dislocation wall and can improve the mechanical properties of such steels
[33,34].

Figure 4.
Figure 4. OM
OM micrographs
micrographs of of tensile
tensile sample
sample cross-sections
cross-sections after
after tensile
tensile fracture:
fracture: (a,b)
(a,b) UC-1.2
UC-1.2 and
and (c–f)
(c–f) C-4.8.
C-4.8. A
A lower
lower
surface tearing
surface tearing (damage)
(damage) isis shown
shown by by white
white arrows.
arrows. Elongated
Elongated melt
melt pool
pool boundaries
boundaries (MPBs)
(MPBs) toward
toward the
the building
building direction
direction
(BD)and
(BD) andloading
loadingdirection
direction(LD)
(LD)areareshown
shownasaswell.
well.Strain
Strain localization
localization and
and crack
crack propagation
propagation toward
toward an an
MPBMPB
are are shown
shown on
on the fracture surface of UC-1.2 (b). Severe surface tearing is shown in (c,d) using white arrows on the pre-charged
the fracture surface of UC-1.2 (b). Severe surface tearing is shown in (c,d) using white arrows on the pre-charged surface.
surface. No detachment of MPBs is shown in (d,f), using white rectangles. Crack-propagation toward the MPB is shown
No detachment of MPBs is shown in (d,f), using white rectangles. Crack-propagation toward the MPB is shown in (e).
in (e). A considerbale rupture can be seen in (f) that seems to be independent of MPBs. A shows the fracture surface and
A considerbale
B is pre-chargedrupture
surface.can be seen in (f) that seems to be independent of MPBs. A shows the fracture surface and B is
pre-charged surface.
The SEM micrographs of tensile fractured surfaces in conjunction with energy-dispersive
X-ray spectroscopy (EDS) analysis are shown in Figures 5 and 6. The fracture surfaces
included both the cleavages and dimples as the characteristics of brittle and ductile fracture
modes, respectively. However, the ductile mode was the dominant fracture mechanism. In
addition, there were some porosities in the fracture surface of the L-PBF samples (white
arrow in Figure 5b). Moreover, the EDS analysis of points A and B in Figure 5b showed that
in point A, beside the voids, a segregation of alloying elements occurred. There was a similar
trend in the case of points A and B in Figure 6 for C-4.8 sample. The segregation of elements
Metals 2021, 11, 586 7 of 12

in L-PBFed stainless steel 316L has been reported many times [33,34]. A high solidification
rate and lack of equal mobility of elements during solidification are the main reasons for
obtaining such elemental segregation that may cause the formation of a dislocation
Metals 2021, 11, x FOR PEER REVIEW wall and
8 of 13
can improve the mechanical properties of such steels [33,34].
Metals 2021, 11, x FOR PEER REVIEW 8 of 13

5. SEM5.images
Figure Figure SEM imagesof the
of fractured surfaces
the fractured surfacesofofUC-1.2
UC-1.2 sample: (a)low
sample: (a) low magnification,
magnification, (b) high
(b) high magnification,
magnification, and (c–e)
and (c–e)
EDS
EDS analysis analysis
Figure of the of
5. SEM the points
images
points theA,
of B,
A, B, C,
and
fractured
and C, respectively,
surfaces
respectively, in (b).
of UC-1.2
in (b). White
sample:
White (a)arrows refertotothe
theporosities.
low magnification,
arrows refer porosities. EDS peaks
peaksare
(b) high magnification,
EDS X-rays
and
are (c–e) given
X-rays
given off as electrons
EDS analysis of the returnA,
points to B,
theand
K electron shell (K-alpha
C, respectively, in (b).(Kα) andarrows
White K-beta refer
(Kβ) lines).
to the porosities. EDS peaks are X-rays
off as electrons return to the K electron shell (K-alpha (K α ) and K-beta (Kβ ) lines).
given off as electrons return to the K electron shell (K-alpha (Kα) and K-beta (Kβ) lines).

Figure 6. SEM images of the fractured surfaces of C-4.8 sample: (a) low magnification, (b) high magnification, and (c) EDS
analysis
6. SEM6.of
Figure Figure the images
SEM
images points A and B, respectively,
of fractured
of the the fractured in
ofof(b).
surfaces
surfaces EDS
C-4.8
C-4.8 peaks (a)
sample:
sample: are X-rays
(a)low given off as(b)
lowmagnification,
magnification, electrons
high return to theand
magnification,
(b) high K electron
magnification, (c)and
EDS(c) EDS
shell (K-alpha
analysis of the(K α) andAK-beta
points and B,(Krespectively,
β) lines). in (b). EDS peaks are X-rays given off as electrons return to the K electron
analysis of the points A and B, respectively, in (b). EDS peaks are X-rays given off as electrons return to the K electron shell
shell (K-alpha (Kα) and K-beta (Kβ) lines).
(K-alpha (Kα ) and K-beta (Kβ ) lines).
 x FOR PEER REVIEW
Metals 2021, 11, 586 98of
of 13
12

4.
4. Discussion
Discussion
In
In this
this study, hydrogen charging
study, hydrogen charging caused
caused aa decrease
decrease in in the ductility of
the ductility of UTS
UTS of 316L
of 316L
ASS based on tensile properties and fracture modes, illustrated in
ASS based on tensile properties and fracture modes, illustrated in Figures 3, 5 and 6, Figures 3, 5 and 6, which
agrees with previous
which agrees reportsreports
with previous [15–17];[15–17];
in which in awhich
suitable performance
a suitable of L-PBFed
performance micro-
of L-PBFed
structures againstagainst
microstructures H was H reported due to the
was reported due presence of the cellular
to the presence of thestructure.
cellular Baek et al.
structure.
[16]—in
Baek et al.the case ofthe
[16]—in 304L—concluded that in thethat
case of 304L—concluded presence
in the of hydrogen,
presence the strain-induced
of hydrogen, the strain-
plasticity transformation
induced plasticity of austenite
transformation to martensite
of austenite is postponed
to martensite in extensive
is postponed strains,
in extensive
which results in larger elongations compared to rolled 304L. According
strains, which results in larger elongations compared to rolled 304L. According to the to the microstruc-
tures of deformed
microstructures ofsamples
deformed andsamples
XRD analysis
and XRD results (see Figures
analysis results 4(see
andFigures
7, respectively),
4 and 7,
the martensitethe
respectively), phase was notphase
martensite observed. Thisobserved.
was not can be explained
This canby be the high content
explained by theof highNi
as a strong
content austenite
of Ni stabilizer,
as a strong where
austenite the Cr amount
stabilizer, where as thea ferrite
Cr amountstabilizer is not more
as a ferrite than
stabilizer
17.3
is notwt.%.
moreAthan slight reduction
17.3 wt.%. Ain UTS*UE
slight after hydrogen
reduction in UTS*UEcharging might be
after hydrogen explained
charging mightby
the HELP mechanism
be explained by the HELP[35], mechanism
although no[35], considerable
although embrittlement
no considerable was observed forwas
embrittlement the
C-1.2 sample.
observed However,
for the increasing
C-1.2 sample. the strain
However, rate caused
increasing a decrease
the strain in the aaverage
rate caused decrease amount
in the
average
of UTS*UE. amount
It was ofalready
UTS*UE. It was already
explained by [20]explained
that a higherby [20] that adensity
current higher cancurrent
cause density
dam-
can cause
age on thedamage
surface onof the
the surface of the
ASSs, and, ASSs, and,
therefore, therefore,
from Figure from Figurethat
3, it seems 3, it the
seems that
surface
the surface
damage damage
caused by acaused
higher by a higher
strain strain
rate was rateeffective
more was more oneffective
the overallon the overall
tensile tensile
behaviour
behaviour
of L-PBFedof L-PBFed
ASS. FigureASS. Figure
8 shows the8presence
shows the of presence
more surfaceof more surface
cracks cracks
(surface (surface
tearing and
tearing and
damage) ondamage) on the longitudinal
the longitudinal direction ofdirection
the broken of the broken
sample. It sample.
should be It should
noted that be noted
such
that such
surface surface
cracks are cracks are independent
independent of the manufacturing
of the manufacturing process, andprocess,
the L-PBF andprior
the L-PBF
to the
prior to the H charging may not be responsible for their formation.
H charging may not be responsible for their formation. Such surface cracks in the Such surface cracks in
longi-
the longitudinal
tudinal directiondirection
of failed of failed
samplessamples
were were
also also detected
detected andand reported
reported inin[25][25]for
for the
the
casted/annealedsamples.
casted/annealed samples.

Figure 7.
Figure XRD analysis
7. XRD analysis of
of C-4.8
C-4.8 sample
sample from
from the
the fractured
fractured zone
zone and
and revealing
revealing of
of austeinte
austeinte peaks.
peaks.
Irrespective of the surface damage caused by H charging that is independent of the
manufacturing process, the origin of the lower UTS*UE of hydrogen-doped 316L ASS can be
explained by the following observations: The MPBs can act as nucleation and propagation
sites for hydrogen-assisted cracking (see Figure 4). Thus, their presence is among the
possible reasons for the lower UTS*UE. It should be noted that no sign of H-assisted cracks
for grain boundary–twin boundary–slip line–mechanical twin interactions was found
in another study [17] for SSs. During the tensile loading, a high density of dislocations
formed by the high cooling rate of solidification [36] could be responsible for H trapping,
and hence, they might have a negative effect on the average UTS*UE amount [37,38]. In
addition, the cellular structure with a high density of dislocation around the cell wall’s
structure can absorb fewer hydrogen atoms, and thus, they might not be responsible for
Metals 2021, 11, 586 9 of 12

the H trapping [17,20]. From all the findings of the current study and the literature, it
can be concluded that the high density of dislocations after L-PBF for H trapping—which
might affect the HELP mechanism as well as the presence of MPBs—is the possible cause
of the slight L-PBF-induced reduction in UTS*UE after H charging on L-PBFed SS 316L. In
addition to L-PBF-induced causes, the surface damage after electrochemical H charging
Metals 2021, 11, x FOR PEER REVIEW 10 ofis13
another important cause of the UTS*UE reduction.

Figure8.8.SEM
Figure SEMimages
imagesof
ofthe
thefractured
fractured surfaces
surfaces from
from longitudinal
longitudinal direction:
direction: (a,b)
(a,b) UC-1.2
UC-1.2 and
and(c,d)
(c,d)
C-4.8, with the same magnification to highlight the number of surface cracks that were detected on
C-4.8, with the same magnification to highlight the number of surface cracks that were detected on
the sample. (b,d) are higher magnification of (a,c), respectively. The yellow rectangles refer to the
the sample. (b,d) are higher magnification of (a,c), respectively. The yellow rectangles refer to the
surface cracks.
surface cracks.
Irrespective of the surface damage caused by H charging that is independent of the
5. Conclusions
manufacturing process, the origin of the lower UTS*UE of hydrogen-doped 316L ASS can
The tensile behavior, microstructures, and fracture surfaces of 316L ASSs produced
be explained by the following observations: The MPBs can act as nucleation and propaga-
by the L-PBF process were compared before and after electrochemical hydrogen charging.
tion sites for hydrogen-assisted cracking (see Figure 4). Thus, their presence is among the
For this purpose, an extreme hydrogen environment including a high current density of
possible reasons for the lower UTS*UE. It should be noted that no sign of H-assisted cracks
100 mA/cm2 was applied for three days. The hydrogen charging caused a minor loss in
for grain boundary–twin boundary–slip line–mechanical twin interactions was found in
the ductility and UTS of the samples. Approximately 3.5% in elongation to failure and
another study [17] for SSs. During the tensile loading, a high density of dislocations
2.1% in the UTS of the samples were obtained using a low strain rate of 1.2 × 10−4 s−1 .
formed by the high cooling rate of solidification [36] could be responsible for H trapping,
It was also found that an increase in the strain rate from 1.2 × 10−4 s−1 to 4.8 × 10−4 s−1
andtohence,
led they might
a reduction have a negative
of approximately 3.6% effect on thefor
on average average UTS*UEtoamount
the elongation [37,38].
failure and 1.7%In
addition,
on averagetheforcellular
the UTS structure with a highsamples,
in the pre-charged density of dislocation
with a higheraround theofcell
detection wall’s
surface
structure can absorb fewer hydrogen atoms, and thus, they might not be responsible
cracks (caused by the electrochemical H charging process) on the broken samples. It was for
the H trapping [17,20]. From all the findings of the current study and the literature, it can
be concluded that the high density of dislocations after L-PBF for H trapping—which
might affect the HELP mechanism as well as the presence of MPBs—is the possible cause
of the slight L-PBF-induced reduction in UTS*UE after H charging on L-PBFed SS 316L.
In addition to L-PBF-induced causes, the surface damage after electrochemical H charging
Metals 2021, 11, 586 10 of 12

found that the MPBs, which are among the specific features of L-PBFed structures, did not
necessarily cause the crack propagation on the pre-charged surfaces. However, the total
reduction in UTS*UE (GPa%) for the samples after being exposed to the extreme hydrogen
environment was minor and based on the XRD results of the fractured sample; the usage of
a high Ni content to stabilize the austenite structure should be mentioned as an important
reason for this minor reduction.

Author Contributions: Conceptualization, F.K., K.R., A.H. and R.T.M.; methodology, F.K. and K.R.;
software, F.K. and K.R.; validation, A.H. and R.T.M.; formal analysis, A.H. and R.T.M.; investigation,
F.K. and K.R.; data curation, F.K. and K.R.; writing—original draft preparation, A.H. and R.T.M.;
writing—review and editing, A.H. and R.T.M. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was funded by Science Foundation Ireland (SFI) grant number 16/RC/3872
and was cofounded under the European Regional Development Fund and by I-Form industry partners.
Data Availability Statement: The raw/processed data required to reproduce these findings cannot
be shared at this time due to legal or ethical reasons.
Acknowledgments: The assistance of staff and technicians in Dublin City University and Water-
ford Institute of Technology is acknowledged. Furthermore, the assistance of the Razi Applied
Science Foundation for the hydrogen charging, tensile test, and microstructural characterization
is acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

Nomenclature

Symbol Meaning
3D 3-Dimensional
ASS Austenitic Stainless Steels
CAD Computer-Aided Design
ED Energy Density
EDS Energy Dispersive X-Ray Spectroscopy
EL Elongation
UE Uniform Elongation
HE Hydrogen Embrittlement
HELP Hydrogen-Enhanced Localized Plasticity
L-PBF Laser-Powder Bed Fusion
L-PBFed Laser-Powder Bed Fusioned
MPB Melt Pool Boundary
OM Optical microscopy
SEM Scanning Electron Microscopy
SSs Stainless Steels
UTS Ultimate Tensile Strength
XRD X-Ray Diffraction
YS Yield Strength

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