metals

Article
Improvement of Strength and Impact Toughness for
Cold-Worked Austenitic Stainless Steels Using a
Surface-Cracking Technique
Kwangyoon Kim 1 , Minha Park 1 , Jaeho Jang 1 , Hyoung Chan Kim 1 , Hyoung-Seok Moon 1 ,
Dong-Ha Lim 1 , Jong Bae Jeon 1 , Se-Hun Kwon 2 , Hyunmyung Kim 3 and Byung Jun Kim 1, *
1 Energy Plant R&D Group, Korea Institute of Industrial Technology, Busan 46938, Korea;
kky0858@kitech.re.kr (K.K.); pmh0812@kitech.re.kr (M.P.); jngjho@kitech.re.kr (J.J.);
chancpu@kitech.re.kr (H.C.K.); hyoungseok.moon@kitech.re.kr (H.-S.M.); dongha4u@kitech.re.kr (D.-H.L.);
jbjeon@kitech.re.kr (J.B.J.)
2 School of Materials Science and Engineering, Pusan National University, Busan 46241, Korea;
sehun@pusan.ac.kr
3 Department of Nuclear & Quantum Engineering, Korea Advanced Institute of Science and Technology,
Daejeon 34141, Korea; h46kim@kaist.ac.kr
* Correspondence: jun7741@kitech.re.kr; Tel.: +82-10-5136-7743




Received: 25 October 2018; Accepted: 9 November 2018; Published: 12 November 2018


Abstract: For cryogenic applications, materials must be cautiously selected because of a drastic
degradation in the mechanical properties of materials when they are exposed to very low
temperatures. We have developed a new technique using a cold-working and surface-cracking
process to overcome such degradation of mechanical properties at low temperatures. This technique
intentionally induced surface-cracks in cold-worked austenitic stainless steels and resulted in a
significant increase in both strength and fracture at low temperatures. According to the microstructure
observations, dissipation of the crack propagation energy with surface-cracks enhanced the impact
toughness, showing a ductile fracture mode in even the cryogenic temperature region. In particular,
we obtained the high strength and toughness materials by a surface-cracking technique at 5%
cold-worked specimen with surface-cracks.

Keywords: cold-working process; surface-cracking process; impact toughness; strength; low

temperatures; austenitic stainless steels

1. Introduction
The study of very low temperature environments in terms of cryogenics is one field in which the
materials play a major part in desirable performances in severe conditions. Cryogenic technologies
have various applications in many different fields such as in the power industry, chemistry, electronics,
manufacturing, transportation, and food processing by refrigeration [1–7]. For cryogenic applications,
materials must be cautiously selected because of a drastic degradation in mechanical properties of
the materials when they are exposed to very low temperatures [8]. Generally, austenitic steels with
face centered cubic (FCC) structures such as stainless steels [9], Al alloys [10], Ni alloys [11], and Ti
alloys [12] are used as low temperature materials because they have high impact toughness at low
temperatures [13–15]. Although these alloys with FCC structure have excellent mechanical properties
at low temperatures, brittle fracture may occur in welds and rectangular structures due to the stress
concentration [16]. A brittle fracture is usually very dangerous because it occurs abruptly with little or
no warning, resulting in serious economic losses and potentially a loss of many lives. Therefore, it is

Metals 2018, 8, 932; doi:10.3390/met8110932 www.mdpi.com/journal/metals

Metals 2018, 8, 932 2 of 15

in high demand to develop new technologies in order to improve the mechanical properties of FCC
alloys for use in severe environments such as in the cryogenics field.
In particular, materials with good mechanical properties are required for use in severe
environments such as the cryogenics field because material characteristics are significantly degraded
and changed at low temperatures. Work hardening, also known as strain hardening or cold-working,
is a method to strengthen a metal by plastic deformation [17–19]. In detail, the strengthening by
cold-working occurs because of a decrease in the mobility of dislocations during plastic deformation
of metals. The strain hardening is caused by an increase in the dislocation density within the austenitic
structure [20]. Furthermore, the strengthening effect by phase transformation in austenitic stainless
steels where the strained-induced martensitic transformation from austenitic phase shows a substantial
strengthening effect [21–25]. It has also been found that the yield and tensile strength of austenite
stainless steels is gradually improved by increasing the cold-working level. Therefore, a cold-working
process is typically considered to be an important technique for increasing the strength of steels [26,27].
However, negative effects such as the unfavorable material embrittlement can be caused by reductions
in ductility and impact toughness after a cold-working process [28].
Generally, impact toughness is reduced with an increase in work hardening and precipitates,
whereas it typically shows a positive correlation with increases in ductility [29]. In recent research,
the grain size refinement was an important technique for improving the impact toughness for
high-strength steels [30–34]. Thermal heat treatments affected enhanced impact toughness by an
ultra-fine grained structure [29]. Another approach to enhancing impact toughness is to provide
multiple pathways for crack propagation, for example, by adding ultra-fine particles within the fine
granular structure. Delamination, or splitting, resulting from anisotropic microstructures such as
crystalline grains and secondary phases is well known to improve the toughness of metals at low
temperatures [23,28,29]. Toughening mechanisms are for distributing the stress near the crack tips
by allowing the delamination fracture of the grains from one another, instead of brittle fractures in
bulk materials [35–37]. Most engineering designs require materials with high strength and impact
toughness to avoid dangerous failure due to brittle fracture at low temperatures [38]. However, it is
difficult to obtain tougher and stronger steels because materials typically show opposing characteristics
for ductility and brittleness. Therefore, the achievement of a simultaneous enhancement of strength
and toughness is a challenge [38,39].
Higher strength and toughness are key requirements for steels used in various structural
applications, such as for aircraft, buildings, and heavy machinery including cryogenics applications,
in order to satisfy the increasing demands for reliability, durability, and safety. Toughness and strength
do not always have opposite characteristics [40,41]. Increasing the toughness of metals without
sacrificing other properties is critical for their economic competitiveness [31,38,42,43]. It is true that
for intrinsically ductile materials, such as metals, the improvement in strength usually comes at the
expense of toughness [44,45]. However, the present results show the possibility and potential of
improving toughness and strength at the same time. In this study, we have developed a new technique
using a cold-working and surface-cracking process to increase the strength and toughness at the same
time. Our proposed method is called a surface-cracking technique which has two processes with the
cold-working and surface-cracking process. Cold-working (CW) is one of the typical methods which
imparts higher strength to steel, but decreases in ductility accompanied by toughness degradation are
generally unavoidable. However, our work shows that enhanced toughness can be achieved using
the surface-cracking technique without sacrificing strength. We applied this technique to austenitic
stainless steels including base metal and weld metal.

2. Materials and Methods

The chemical compositions of stainless steels used in this study are shown in Table 1. A thick
plate of STS304 was welded with a STS308L welding electrode (ESAB SEAH, Gyeongnam, Korea) by
the submerged-arc welding (SAW) method. The dimension of the welded plate was in the width of
Metals 2018, 8, 932 3 of 15

100 mm, the length of 1000 mm, and the thickness of 25 mm. For the post-weld heat treatment (PWHT),
the austenitic stainless steels were processed at 105 ◦ C for 2 h, and subsequently quenched in water.
Metals 2018, 8, x FOR PEER REVIEW
In order to observe the microstructures, the test samples were mechanically polished using a3 2000 of 15
grit
SiC paper and then micro-polished using a 3 µm and 1 µm diamond paste. Then,
in water. In order to observe the microstructures, the test samples were mechanically polished using
sample surfaces
were aetched in aSiC
2000 grit solution containing
paper and 40% distilled
then micro-polished water,
using 30%
a 3 μm HNO
and 1 μm 3 , diamond
and 30%paste.NO3 .Then, sample
Tensile
surfacestesting was carried
were etched out at
in a solution room temperature
containing 40% distilledusing
water,a 530%
kNHNO full-automatic
3, and 30% NOINSTRON
3. 4204
tensile machine
Tensile(INSTRON, Norwood,
testing was carried out atMA,
roomUSA) at a cross
temperature head
using a 5speed of 0.03 mm/s.
kN full-automatic The dimensions
INSTRON 4204
of thetensile machine (INSTRON,
miniaturized Norwood,were
tensile specimens MA, USA)
5 mmatin a cross
gaugehead speed of
length, 1.20.03
mm mm/s. The dimensions
in width, and 0.5 mm
of the
in thickness. miniaturized tensile specimens were 5 mm in gauge length, 1.2 mm in width, and 0.5 mm in
thickness.
Table 1. The chemical compositions of the specimens used in this study (wt %).
Table 1. The chemical compositions of the specimens used in this study (wt %).
Alloys C Mn Si Cr Ni Mo Al Cu Fe
Base Alloys
Metal (STS304) C
0.046 Mn
1.19 Si
0.42 Cr
18.23 Ni
8.02 Mo
0.149 Al
0.003 Cu
0.223 Bal.Fe
Weld Metal (STS308L) 0.02 1.98 0.41 19.71 10.79 0.03 - 0.13 Bal.
Base Metal (STS304) 0.046 1.19 0.42 18.23 8.02 0.149 0.003 0.223 Bal.

Weld Metal (STS308L) 0.02 1.98 0.41 19.71 10.79 0.03 - 0.13 Bal.
Vickers hardness tests were performed at room temperature with a load of 4.95 N with 10 s of
dwell time. At least 10 measurements were made to calculate the average micro-hardness values by
Vickers hardness tests were performed at room temperature with a load of 4.95 N with 10 s of
excluding the
dwell time. minimum
At least 10value and maximum
measurements were madevalue.to We prepared
calculate Charpy
the average V-notch impact
micro-hardness specimens
values by
(10.0 mm × 10.0 mm × 55.0 mm) without or with surface-cracks to evaluate
excluding the minimum value and maximum value. We prepared Charpy V-notch impact specimensthe improvement of impact
toughness
(10.0 mmby surface-cracks (Figure
× 10.0 mm × 55.0 mm) 1). Charpy
without V-notch impact
or with surface-cracks tests were
to evaluate the performed
improvement toofmeasure
impact the
toughness
absorbed energy byatsurface-cracks
temperatures (Figure
from 1).
20 Charpy ◦ C using
to −180V-notch impact tests were performed
a full-automatic to measure
Zwick Charpy the test
impact
absorbed
machine energy(Zwick/Roell,
according at temperaturesUlm,
fromGermany)
20 to −180 °C tousing
ASTM a full-automatic
E23 [46]. Zwick Charpy impact test
machine
Our according
proposed (Zwick/Roell,
method Ulm,
is called Germany) to ASTMtechnique
a surface-cracking E23 [46]. which involves two processes
Our proposed method is called a surface-cracking technique which involves two processes
including a cold-working and a surface-cracking process. The first step was a typical method for
including a cold-working and a surface-cracking process. The first step was a typical method for
improving the strength of stainless steel by a cold-working process. From the as-received (AS)
improving the strength of stainless steel by a cold-working process. From the as-received (AS)
STS304, a plate of steel with 20 mm thickness was cold worked into different thicknesses of the plates
STS304, a plate of steel with 20 mm thickness was cold worked into different thicknesses of the plates
CW05, CW10,
CW05, CW10, andand
CW30,CW30,with
withreductions
reductionsof ofplate
plate thickness
thickness byby5,5,1010
andand 30%,
30%, respectively.
respectively. In order
In order
to minimize
to minimizethe the
effect of directionality
effect of directionalityby bycold-working,
cold-working, aa cold-working
cold-working process
process waswas performed
performed
several timestimes
several at the same
at the thickness
same thicknessreduction
reductionrate
rate in both
boththe
thelongitudinal
longitudinal andand transverse
transverse directions.
directions.
The configurations and process conditions of the test specimens used in this
The configurations and process conditions of the test specimens used this study are summarized in study are summarized
Tablein2. Table 2.

Figure 1. Configurations
Figure 1. Configurationsof
of the
the specimens usedinin
specimens used this
this study.
study.

The second stepstep

The second waswas
a surface-cracking
a surface-crackingprocess for improving
process for improvingthethe impact
impact toughness
toughness of stainless
of stainless
steel by
steelinducing thethe
by inducing surface-cracks
surface-cracksonon the specimen
specimensurface.
surface. This
This method
method was applied
was applied to Charpy
to Charpy V-
V-notch impact test specimens to evaluate the enhancement of impact toughness for stainlessInsteels.
notch impact test specimens to evaluate the enhancement of impact toughness for stainless steels.
this
In this method,surface-cracks
method, surface-cracks were
wereformed
formed in in
thethe
direction perpendicular
direction to theto
perpendicular V-notch direction
the V-notch by
direction
wire cut machining V850G (EXCETEK, Taichung, Taiwan). This work was machined to a depth of 0.1
by wire cut machining V850G (EXCETEK, Taichung, Taiwan). This work was machined to a depth
mm to disperse the tri-axial stress at the V-notch tip using a wire with a width of 0.3 mm (as shown
surface-cracking technique is shown in Figure 2.

Table 2. Configurations of the specimens used in this study.

Specimen ID
Metals 2018, 8, 932
Region Cold-Working Level Number of Added Surface-Cracks
4 of 15

BM-AS Base metal - -

of 0.1 mm to disperse the
BM-AS-L5 tri-axial
Base metal stress at the V-notch
- tip using a wire with a width of 0.3 mm (as
5 lines
shown in Figure 1). In order to observe the effect of surface-cracks, surface-cracks were fabricated with
5 and BM-AS-L10 Base metal
10 lines and compared -
with standard specimens without surface-cracks.10The
lines
overall process of a
surface-cracking
BM-CW05 technique is shown
Base metal in Figure 2.
5% -

BM-CW05-L10 Base
Tablemetal
2. Configurations of5% 10 lines
the specimens used in this study.

BM-CW10
Specimen ID Base Region
metal 10%
Cold-Working Level Number of Added- Surface-Cracks
BM-AS
BM-CW10-L10 Base
Base metal
metal 10%- 10 -lines
BM-AS-L5 Base metal - 5 lines
BM-AS-L10
BM-CW30 Base
Base metal
metal 30%- 10 lines
-
BM-CW05 Base metal 5% -
BM-CW05-L10
BM-CW30-L10 Base
Base metal
metal 30%5% 10
10lines
lines
BM-CW10 Base metal 10% -
WM
BM-CW10-L10 Weld metal
Base metal - 10% -
10 lines
BM-CW30 Base metal 30% -
WM-L5
BM-CW30-L10 Weld metal
Base metal - 30% 5 lines
10 lines
WM Weld metal - -
WM-L10
WM-L5 Weld metal
Weld metal - - 10 lines
5 lines
WM-L10 Weld metal - 10 lines
To analyze the phase transformation of austenitic stainless steels after a cold-working process,
the volume fraction
To analyze of martensite
the phase was measured
transformation by a stainless
of austenitic FERITSCOPEsteelsFMP30 (Fischer, Windsor,
after a cold-working CT,
process,
USA).
the The volume
volume fractionfraction was measured
of martensite 8 timesby
was measured per specimen in total.
a FERITSCOPE The(Fischer,
FMP30 fracture surface
Windsor,ofCT,
the
Charpy
USA). Theimpact
volume testfraction
specimen
waswas observed
measured withper
8 times a FE-SEM
specimen HITACHI S-4800
in total. The (HITACHI,
fracture surfaceTokyo,
of the
Japan). impact test specimen was observed with a FE-SEM HITACHI S-4800 (HITACHI, Tokyo, Japan).
Charpy

Figure2.2.Schematic
Figure Schematicdiagram
diagramof
ofaasurface-cracking
surface-crackingtechnique.
technique.

3. Results and Discussion

3.1. Strengthening by a Cold-Working Process

Figure 3 shows the microstructure of base metal for austenitic stainless steel STS304 before and
after a cold-working process. The microstructure of the base metal before cold-working was typically
an austenitic structure with 160 µm grain size, as shown in Figure 3a. After the cold-working process,
the microstructure was changed from austenite single phase to dual phases which consisted of austenite
3.
3.Results
Resultsand
andDiscussion
Discussion

3.1.
3.1.Strengthening
Strengtheningby
byaaCold-Working
Cold-WorkingProcess
Process
Figure
Figure 33 shows
shows the
the microstructure
microstructure of of base
base metal
metal for
for austenitic
austenitic stainless
stainless steel
steel STS304
STS304 before
before andand
after
afteraa cold-working
cold-working
Metals 2018, 8, 932
process.
process. The
Themicrostructure
microstructure of
of the
the base
base metal
metalbefore
before cold-working
cold-working was
was typically
typically
5 of 15
an
anaustenitic
austeniticstructure
structurewith
with160
160μmμmgrain
grainsize,
size,as
asshown
shownin inFigure
Figure3a.
3a.After
Afterthe
thecold-working
cold-workingprocess,
process,
the
the microstructure
microstructure was was changed
changed from
from austenite
austenite single
single phase
phase to
to dual
dual phases
phases which
which consisted
consisted of of
and martensite
austenite
austenite and (Figure 3b–d).
and martensite
martensite (Figure
(FigureThe fraction
3b–d).
3b–d). The of martensitic
The fraction
fraction of phase increased
of martensitic
martensitic phase with anwith
phase increased
increased increase
with an in the
an increase
increase
cold-working
in
inthe
thecold-workinglevel from
cold-working level5%
level fromto 30%.
from 5%
5%to
to30%.
30%.

Figure
Figure3.3.The
Themicrostructure
microstructureof
ofthe
thebase
basemetal
metalfor
foraustenitic
austeniticstainless
stainlesssteel
steelSTS304
STS304before
beforeand
andafter
afteraa
cold-workingprocess:
cold-working process:(a)
(a)AS-BM,
AS-BM,(b)
(b)BM-CW05,
BM-CW05,(c) BM-CW10,
(c)BM-CW10,
BM-CW10,and and (d)
and(d) BM-CW30.
(d)BM-CW30.
BM-CW30.

Figure
Figure444shows
Figure shows
shows the
theresults
the of tensile
results
results of properties
of tensile
tensile for STS304
properties
properties for beforebefore
for STS304
STS304 and after
before and
anda cold-working
after process.
after aa cold-working
cold-working
The ultimate
process. The tensile
ultimate strength
tensile (UTS)
strength of highly
(UTS) cold-worked
of highly steel
cold-worked (BM-CW30)
steel with
(BM-CW30)
process. The ultimate tensile strength (UTS) of highly cold-worked steel (BM-CW30) with a reduction a reduction
with a of plate
reduction
thickness
of
ofplate by 30% was
platethickness
thickness by
by30% about
30% was
wastwo times
about
about two
twohigher
timesthan
times higherthat
higher of the
than
than thatas-received
that of
ofthe steels (BM-AS).
theas-received
as-received steels The tensile
steels(BM-AS).
(BM-AS). The
The
strength
tensile of cold-worked
tensile strength
strength of steels increased
of cold-worked
cold-worked steels with anwith
steels increased
increased increase
with an of the cold-working
an increase
increase of
of the level from
the cold-working
cold-working level5%from
level to 30%.
from 5%
5%
However,
to
to30%. the
30%.However, elongation
However,the of cold-worked
theelongation
elongationof steels
ofcold-worked decreased
cold-workedsteels with
steelsdecreased reductions
decreasedwith in ductility.
withreductions
reductionsin inductility.
ductility.

Figure
Figure4.4.The
Thestress-strain
stress-straincurves
curvesof
ofSTS304
STS304before
beforeand
andafter
afteraacold-working process.
cold-workingprocess.
process.

3.2. Mechanism of Strengthening of a Cold-Working Process

Cold-working generally leads to an increase in the yield strength of stainless steels because of
the increased number of dislocations [43]. Figure 5 shows the results of the quantitative analysis for
the martensite volume fraction measured by the ferrite scope. As-received steels (BM-AS) with a fully
austenite structure were close to a 0% volume fraction of martensite. The volume fraction of martensite
increased with the cold-working level from 5% to 30% (Figure 5). In the case of 30% cold-worked
specimens (BM-CW30), the volume fraction of martensite increased to about 8%. Therefore, strength
3.2. Mechanism
Cold-working of Strengthening of a Cold-Working
generally leads to an increaseProcess
in the yield strength of stainless steels because of
the increased
Cold-workingnumber of dislocations
generally leads to[43]. Figure 5inshows
an increase the results
the yield strengthof of
thestainless
quantitative
steelsanalysis
becauseforof
the martensite volume fraction measured by the ferrite scope. As-received steels (BM-AS)
increased number of dislocations [43]. Figure 5 shows the results of the quantitative analysis for with a fully
austenite
the martensitestructure
volume were closemeasured
fraction to a 0% byvolume fraction
the ferrite scope.ofAs-received
martensite.steels
The (BM-AS)
volume with
fraction of
a fully
martensite
austenite
Metals
increased
2018, 8,structure
932
with the cold-working level from 5% to 30% (Figure 5). In the
were close to a 0% volume fraction of martensite. The volume fraction case of 30% cold-
of
6 of 15
worked
martensite specimens
increased (BM-CW30), the volume level
with the cold-working fraction
fromof 5%
martensite increased
to 30% (Figure 5). to
In about 8%.
the case ofTherefore,
30% cold-
strength was increased
worked specimens by the phase
(BM-CW30), transformation
the volume fraction from austeniteincreased
of martensite to martensite and 8%.
to about the increase in
Therefore,
was increased
dislocations by
by the phase
plastic transformation
deformation [20]. from austenite to martensite and the increase
strength was increased by the phase transformation from austenite to martensite and the increase in in dislocations
by plastic deformation
dislocations by plastic [20].
deformation [20].

Figure 5. Martensite volume fractions (in %) of STS304 before and after a cold-working process.
Figure 5. Martensite
Figure 5. Martensite volume
volume fractions
fractions (in
(in %)
%) of
of STS304
STS304 before
before and
and after
afteraacold-working
cold-workingprocess.
process.
Figure 6 shows the result of the Vickers hardness test before and after a cold-working process.
Figure
Figure 66 shows
The hardness value of
shows the
the result
result of
of the
as-received Vickers
steel
the (BM-AS)
Vickers hardness test
was about
hardness test before
161 HV.
before and after
Similar
and after toaa cold-working
the tensile testprocess.
cold-working results,
process.
The hardness
hardness
The hardness value
values of as-received
increased
value steel
with an steel
of as-received (BM-AS)
increase was
in thewas
(BM-AS) about
levelabout 161 HV. Similar
of cold-working. Theto
161 HV. Similar to the
the tensile
increase test
of the
tensile results,
hardness
test results,
hardness
value values
after a increased
cold-working with an
process increase
was in
owed the tolevel
the of
samecold-working.
mechanism The
as increase
that
hardness values increased with an increase in the level of cold-working. The increase of the hardness in the of the hardness
tensile results
value
which after a
have athe
value after cold-working process
phase transformation
cold-working process waswas owed
of martensite to
owed to the the same
fromsame mechanism
austenite and the
mechanism as that
asincrease in
that in the the tensile results
in dislocations by
tensile results
which
whichhave
plastic have the
thephase
deformation. transformation
phaseTherefore, results
transformation of martensite
offrom tensilefrom
martensite austenite
and hardness
from and
and the
austenitetests were
the increase
in good
increase in dislocations
inagreement
dislocations by
with
by
plastic deformation.
quantitative analysis Therefore,
of the results
volume from
fraction tensile
of and
martensite hardness
as tests
measured were
by
plastic deformation. Therefore, results from tensile and hardness tests were in good agreement with in
the good
ferrite agreement
scope. with
Table 3
quantitative
summarizes analysis of the
the test results
quantitative analysis volume fraction
of the tensile
of the volume fraction of martensite
properties
of martensite as measured
and Vickers by
hardness
as measured the
by the ferrite
values
ferrite scope.
obtained Table 3
in this3
scope. Table
summarizes
work. the test results of the tensile properties and Vickers hardness
summarizes the test results of the tensile properties and Vickers hardness values obtained in values obtained in this work.
this
work.

Figure 6. Hardness
Figure 6. Hardness of
of STS304
STS304 before
before and
and after
after aa cold-working
cold-workingprocess.
process.
Figure
Table 3. Tensile 6. Hardness
properties andof STS304
Vickers before and
hardness afterofathe
values cold-working process.
specimens used in this study.

Yield Strength, σy Tensile Strength, Average Vickers

Specimen ID Elongation, (%)
(MPa) σt (MPa) Hardness (HV)
BM-AS 212 689 91 161
BM-CW05 548 848 70 237
BM-CW10 611 854 56 286
BM-CW30 1002 1053 17 330
 BM-AS 212 689 91 161

BM-CW05 548 848 70 237

BM-CW10 611 854 56 286

Metals 2018, 8, 932 7 of 15
BM-CW30 1002 1053 17 330

3.3. Toughening
Toughening by
by aa Surface-Cracking
Surface-Cracking Process
Process
Generally,
Generally, ordinary
ordinary cracks
cracks in in materials
materials weaken
weaken their
their mechanical
mechanical characteristics
characteristics due to the stress
concentration at crack tips. Although
Although the the presence
presence of of flaws or cracks causes fractures due to the
concentration of stress, a number of aligned cracks in a matrix can distribute the fracture energy in
reverse.
reverse. The
Theabsorbed
absorbedenergy
energy vs.vs.testtest
temperature
temperature curves for specimens
curves with a with
for specimens surface-cracking process
a surface-cracking
is shown in Figure 7. At room temperature, the absorbed energy of as-received
process is shown in Figure 7. At room temperature, the absorbed energy of as-received specimens specimens was about
400
wasJ.about
Although
400 J.austenite
Althoughstainless
austenitesteel with face
stainless steelcentered
with facecubic (FCC)
centered structure
cubic (FCC) does not show
structure does the
not
ductile-to-brittle temperature (DBTT) behavior, the absorbed energy tends to decrease
show the ductile-to-brittle temperature (DBTT) behavior, the absorbed energy tends to decrease with with decreasing
temperature. In the case ofInspecimens
decreasing temperature. the case with surface-cracks,
of specimens the absorbed energy
with surface-cracks, was almost
the absorbed the same
energy was
comparing
almost the the
same as-received
comparing specimen at room specimen
the as-received temperature. However,
at room the specimen
temperature. with surface-cracks
However, the specimen
had
witha surface-cracks
higher absorbed energy
had compared
a higher absorbedto the as-received
energy specimen
compared to thewithout surface-cracks
as-received specimenatwithout
the low
◦
temperature
surface-cracksregion
at the low−temperature
(below 60 C) As the regionnumber(below
of surface-cracks
−60 °C) As increased from 0 lines
the number (as-received)
of surface-cracks
to 10 lines,from
the absorbed energy significantly increased at below ◦ C. At a very low temperature
−60significantly
increased 0 lines (as-received) to 10 lines, the absorbed energy increased at below
−180
(−60 ◦
°C. C),
At the absorbed
a very energy of the
low temperature specimen
(−180 °C), thewith 10 surface-cracks
absorbed energy of the (BM-AS-L10)
specimen with was10 two times
surface-
higher
cracks than that of thewas
(BM-AS-L10) as-received
two times specimen
higher without
than that surface-cracks. Therefore,
of the as-received this effect
specimen of enhanced
without surface-
toughness by a surface-cracking
cracks. Therefore, this effect of process
enhanced occurred at very
toughness by low temperatures when
a surface-cracking the material
process occurredchanged
at very
to having brittle properties.
low temperatures when the material changed to having brittle properties.

Figure
Figure 7. The absorbed
7. The absorbed energy
energy vs. test temperature
vs. test temperature curves
curves for
for specimens
specimens with
with surface-cracks.
surface-cracks.

3.4. Toughening by a Surface-Cracking Process

3.4. Toughening by a Surface-Cracking Process
Figure 8 shows the fracture shape of as-received specimens and specimens with surface-cracks
Figure 8 shows the fracture shape of as-received specimens and specimens with surface-cracks
after the Charpy impact test. The facture shape of all specimens with or without surface-cracks
after the Charpy impact test. The facture shape of all specimens with or without surface-cracks
observed large plastic deformation at room temperature (Figure 8a–c). There was no significant
observed large plastic deformation at room temperature (Figure 8a–c). There was no significant
difference between the as-received specimens and specimens with surface-cracks near the V-notch.
difference between the as-received specimens and specimens with surface-cracks near the V-notch.
We also could not observe any differences in plastic deformation by the number of micro-cracks.
However, the effect of surface-cracks was clearly observed at the cryogenic temperature (−180 ◦ C)
(Figure 8d–f). Compared to the results at room temperature, as-received specimens were completely
fractured and accompanied with slight plastic deformation at the cryogenic temperature (Figure 8d).
However, the specimens with surface-cracks significantly increased plastic deformation around the
V-notch and surface-cracks. The plastic deformation also increased with the increasing number of
surface-cracks. From the results of the Charpy impact test in Figure 7, the effect of surface-cracks could
be confirmed through the fractured formations. Therefore, the fracture shape of the fractured Charpy
specimens was in good agreement with the results of the absorbed energy from the Charpy impact test
at room temperature and cryogenic temperature.
However, the specimens with surface-cracks significantly increased plastic deformation around the
V-notch and surface-cracks. The plastic deformation also increased with the increasing number of
surface-cracks. From the results of the Charpy impact test in Figure 7, the effect of surface-cracks
could be confirmed through the fractured formations. Therefore, the fracture shape of the fractured
Charpy
Metals specimens
2018, 8, 932 was in good agreement with the results of the absorbed energy from the Charpy
8 of 15
impact test at room temperature and cryogenic temperature.

Figure 8. The fracture shape of the as-received specimen and the specimen with surface-cracks after
Figure 8. The fracture shape of the as-received specimen and the specimen with surface-cracks after
Charpy impact test at room temperature (20 ◦ C) and cryogenic temperature (−180 ◦ C): (a) BM-AS
Charpy impact test at room temperature (20 °C) and cryogenic temperature (−180 °C): (a) BM-AS (20
(20 ◦ C), (b) BM-AS-L5 (20 ◦ C), (c) BM-AS-L10 (20 ◦ C), (d) BM-AS (−180 ◦ C), (e) BM-AS-L5 (−180 ◦ C),
°C), (b) BM-AS-L5 (20 °C), (c) BM-AS-L10 (20 °C), (d) BM-AS (−180 °C), (e) BM-AS-L5 (−180 °C), and
and (f) BM-AS-L10 (−180 ◦ C).
(f) BM-AS-L10 (−180 °C).
Figure 9 shows the fracture surface of as-received specimens and specimens with surface-cracks at
20 ◦ C.Figure 9 shows
The facture the fracture
surface surface ofwith
of all specimens as-received
or without specimens and specimens
surface-cracks with observed
was typically surface-cracks
with
at 20 °C. The facture surface of all specimens with or without surface-cracks was
ductile fracture by large plastic deformation at room temperature. There was no significant difference in typically observed
with
the ductile
overall fracture
fracture by large
surface due toplastic deformation
the large deformation at around
room temperature.
the V-notch inThere was no significant
all specimens. The effect
difference in the overall fracture surface due to the large deformation
of enhanced toughness by a surface-cracking process did not happen in room temperature around the V-notch in all
regions
specimens.
with The effect
high ductility of enhanced
properties. Sincetoughness by a surface-cracking
plastic deformation completelyprocess
occurred did not happen
around V-notch in tip
roomat
temperature regions with high ductility properties. Since plastic deformation
room temperature, the additional effect of stress dissipation from the surface-cracks was not significant. completely occurred
around10
Figure V-notch
shows tip the at room temperature,
fracture the additional
surface of as-received specimenseffect and
of stress dissipation
specimens with from the surface-
surface-cracks at
cracks ◦ was not significant. Figure 10 shows the fracture surface
−180 C. The fracture surface of the as-received specimen showed the mixed fracture modes, bothof as-received specimens and
specimens
ductile and with surface-cracks
brittle, at −180
at −180 ◦ C (Figure °C.because
10a) The fracture
it became surface
veryof the as-received
brittle specimen showed
in the low temperature region
the mixed fracture modes, both ductile and brittle, at −180 °C (Figure
despite the ductile behavior at room temperature. However, the fracture mode with surface-cracks 10a) because it became very
brittle
was in the low temperature
predominantly the ductileregion
mode at despite the ductile
very low behavior
temperatures (as at roomintemperature.
shown Figure 10b–c). However,
The ratetheof
fracture mode with surface-cracks was predominantly the ductile mode at
ductile fracture increased with the increasing number of surface-cracks. The fracture surface of thevery low temperatures (as
shown in Figure
as-received 10b–c).
specimen The rateshort
observed of ductile fracture
stretch zones increased
by blunting with
at the
the increasing
V-notch tipnumber
(Figureof10a,
surface-
left).
cracks. The
However, thefracture
fracturesurface
surfaceofofthe as-received
specimens withspecimen
surface-cracksobserved
showedshortthestretch
largestzones by blunting
extension of stretchat
the V-notch tip (Figure 10a, left). However, the fracture surface of specimens
zones near the V-notch and surface-cracks, and ductile tearing occurred at very low temperatures with surface-cracks
showed10c,
(Figure the left).
largest extension
This indicatesofthat
stretch zonessurface-cracks
vertical near the V-notch and
in the surface-cracks,
V-notch directionandserve ductile tearing
to distribute
occurred at very low temperatures (Figure 10c, left).
the stress by increasing the blunting effect at the V-notch tip. This indicates that vertical surface-cracks in the
V-notch direction serve to distribute the stress by increasing the blunting effect
Here, toughening by a surface-cracking process could be explained by the effects of the stress at the V-notch tip.
Here, toughening
dissipation by a surface-cracking
induced by surface-cracks near theprocess
V-notchcould be example,
tip. For explainedaby the effects
number of the stress
of surface-cracks
dissipation induced by surface-cracks near the V-notch tip. For example, a number of surface-cracks
induced by a surface-cracking process led to the enhancement of impact toughness around the V-notch
induced by a surface-cracking process led to the enhancement of impact toughness around the V-
where the surface-cracks in the vertical direction to the V-notch acted as barriers to propagate the
notch where the surface-cracks in the vertical direction to the V-notch acted as barriers to propagate
main crack and disperse the principal stresses of the V-notch. As the number of surface-cracks
the main crack and disperse the principal stresses of the V-notch. As the number of surface-cracks
increased, the absorbed energy increased with an increase in the dissipation of the crack propagation
increased, the absorbed energy increased with an increase in the dissipation of the crack propagation
energy (Figures 7–10). In other words, impact toughness was enhanced by the change in the stress
energy (Figures 7–10). In other words, impact toughness was enhanced by the change in the stress
condition from a plain strain to a plain stress condition due to the reduction of effective thickness by
surface-cracks at the V-notch tip. Therefore, the dissipation of the crack propagation energy in the
materials with surface-cracks enhanced the impact toughness, showing a ductile fracture mode in the
cryogenic temperature region.
Metals 2018, 8, x FOR PEER REVIEW 9 of 15

condition from a plain strain to a plain stress condition due to the reduction of effective thickness by
Metals 2018, 8, x FOR PEER REVIEW 9 of 15
surface-cracks at the V-notch tip. Therefore, the dissipation of the crack propagation energy in the
materials
condition with
from
Metals 2018,
surface-cracks
a plain strain toenhanced
8, 932
the condition
a plain stress impact toughness, showing aofductile
due to the reduction fracture
effective mode
thickness by in the
9 of 15
cryogenic temperature
surface-cracks region.tip. Therefore, the dissipation of the crack propagation energy in the
at the V-notch
materials with surface-cracks enhanced the impact toughness, showing a ductile fracture mode in the
cryogenic temperature region.

Figure 9.9.The
Figure
Figure The fracture
9. The
fracture surface
fracturesurface ofofthe
surface as-received
ofthe
the specimen
as-received
as-received andand
specimen
specimen thethe
and specimen with
specimen
the surface-cracks
with
specimen at at at
surface-cracks
with surface-cracks
room temperature (20 ◦
°C): (a) BM-AS, (b) BM-AS-L5, and (c) BM-AS-L10.
roomroom temperature
temperature (20(20
°C):C):
(a)(a)BM-AS,
BM-AS,(b) (b)BM-AS-L5,
BM-AS-L5, and
and(c)(c)BM-AS-L10.
BM-AS-L10.

Figure
Figure TheThe
10.10. fracture
fracture surface
surface of the
of the as-received
as-received specimen
specimen andand
thethe specimen
specimen with
with surface-cracks
surface-cracks at at
cryogenic temperature ( − 180 ◦ C): (a) BM-AS, (b) BM-AS-L5, and (c) BM-AS-L10.
cryogenic temperature (−180 °C): (a) BM-AS, (b) BM-AS-L5, and (c) BM-AS-L10.

Figure 10. The fracture surface of the as-received specimen and the specimen with surface-cracks at
cryogenic temperature (−180 °C): (a) BM-AS, (b) BM-AS-L5, and (c) BM-AS-L10.
 Metals 2018, 8, 932 10 of 15
Metals 2018, 8, x FOR PEER REVIEW 10 of 15

3.5. High Strength and Toughness Steels by a Surface-Cracking Technique

3.5. High Strength and Toughness Steels by a Surface-Cracking Technique
The absorbed energy vs. test temperature curves for cold-worked steels are shown in Figure 11.
The absorbed energy vs. test temperature curves for cold-worked steels are shown in Figure 11.
At room temperature, the absorbed energy of cold-worked steels decreased with a cold-working
At room temperature, the absorbed energy of cold-worked steels decreased with a cold-working
process. The absorbed energy also decreased with the cold-working level from 5% to 30% (solid
process. The absorbed energy also decreased with the cold-working level from 5% to 30% (solid lines
lines in Figure 11). As we have already mentioned in the Section 3.2, austenite stainless steels after
in Figure 11). As we have already mentioned in the Section 3.2, austenite stainless steels after a cold-
a cold-working process generally resulted in a higher yield strength and lower ductility owing
working process in
to the increase generally resulted
dislocation in and
density a higher yield strength
martensitic and lower
transformation from ductility owing
the austenite to the
phase.
increase in dislocation density and martensitic transformation from the austenite
Therefore, the result of the Charpy impact test provided the decrease in absorbed energy due phase. Therefore,
thetoresult of the Charpy
the reduction impactbytest
of ductility provided the process.
a cold-working decrease in Whenabsorbed energy
comparing thedue to the reduction
surface-cracking
of effect
ductility by a cold-working process. When comparing the surface-cracking effect
in the same cold-working level, the absorbed energy of the specimen with surface-cracks in the same cold-
working
was aboutlevel,
two thetimes
absorbed
higherenergy of the
than that specimen
of the with
specimen surface-cracks
without was about
surface-cracks at lowtwo times higher
temperatures
than of the◦
(below −60 C). In particular, strength and toughness were simultaneously increased inparticular,
that specimen without surface-cracks at low temperatures (below −60 °C). In the 5%
strength and toughness
cold-worked specimen with weresurface-cracks.
simultaneously Theincreased
interesting inthing
the 5%
was cold-worked
that the effectspecimen
of enhancedwith
surface-cracks.
toughness by The interesting thing
a surface-cracking was thathappened
technique the effect at
of all
enhanced toughness
temperature regionsbybya surface-cracking
excluding the
technique happened
as-received at all temperature regions by excluding the as-received results (BM-AS).
results (BM-AS).

TheThe
Figure11.11.
Figure absorbed
absorbed energy
energy vs. temperature
vs. test test temperature
curvescurves for cold-worked
for cold-worked steels steels
with awith a
surface-
surface-cracking
cracking technique.technique.

Figure 12 shows the fracture surface of cold-worked specimens with surface-cracks at 20 ◦ C.

Figure 12 shows the fracture surface of cold-worked specimens with surface-cracks at 20 °C. The
The as-received specimen was fractured in ductile modes by large plastic deformation (Figure 9),
as-received specimen was fractured in ductile modes by large plastic deformation (Figure 9), while
while cold-worked steel appeared to be in a mixture of brittle and ductile modes, showing both cleavage
cold-worked steel appeared to be in a mixture of brittle and ductile modes, showing both cleavage
facets and dimples (Figure 12a,c,e). The fraction of brittle fracture increased with the cold-working level
facets
fromand dimples
5% to 30% at (Figure 12a,c,e). The
room temperature. fractioninofcase
However, brittle fracture
of the increased
cold-worked steelswith
withthe cold-working
surface-cracks,
level from 5% to 30% at room temperature. However, in case of the cold-worked steels with surface-
the fraction of the ductile fracture increased due to the effect of surface-cracks after the surface-cracking
cracks, the fraction
technique of the ductile
(Figure 12b,d,f). Figurefracture
13 shows increased duesurface
the fracture to the of effect of surface-cracks
cold-worked specimensafter
withthe
surface-cracking
surface-cracks attechnique ◦ (Figurebrittle
−180 C. Mostly 12b,d,f). Figure
fracture and a13small
shows the fracture
proportion surface
of dimples wereof observed
cold-worked
in
specimens with surface-cracks at −180 °C. Mostly brittle fracture and a small
the 5% and 10% cold-worked specimens without surface-cracks (Figure 13a,c), and 30% cold-worked proportion of dimples
were observed
specimens in showed
also the 5% and 10%brittle
almost cold-worked
fracturesspecimens
as shownwithout
in Figure surface-cracks
13e. However, (Figure
in case13a,c), and
of the
30% cold-worked
cold-worked specimens
steels also showedthe
with surface-cracks, almost brittle
fraction fractures
of ductile as shown
fracture in Figure
increased due 13e.
to theHowever,
effect
in of
case of the cold-worked
surface-cracks steels with surface-cracks,
after a surface-cracking technique eventhe fraction
at very lowof ductile fracture(Figure
temperatures increased due to
13b,d,f).
theTherefore,
effect of the
surface-cracks
results of theafter a surface-cracking
Charpy impact test and technique evenanalysis
fracture surface at very low
weretemperatures (Figure
in good agreement
with the
13b,d,f). effect of enhanced
Therefore, impact
the results toughness
of the by a surface-cracking
Charpy impact test and fracture technique.
surface analysis were in good
agreement with the effect of enhanced impact toughness by a surface-cracking technique.
Metals 2018, 8, 932 11 of 15
Metals 2018, 8, x FOR PEER REVIEW 11 of 15

12. Fracture
Figure 12. Fracture surface
surface of
of cold-worked
cold-worked specimens
specimens without
without or
or with
with surface-cracks
surface-cracks at room
temperature
temperature (20(20◦ C):
°C):(a)
(a)BM-CW05,
BM-CW05, (b)(b) BM-CW05-L10,
BM-CW05-L10, (c) BM-CW10,
(c) BM-CW10, (d) BM-CW10-L10,
(d) BM-CW10-L10, (e) BM-
(e) BM-CW30,
CW30,
and (f) and (f) BM-CW30-L10.
BM-CW30-L10.

13. Fracture surface of cold-worked specimens without or with surface-cracks at cryogenic

Figure 13.
Figure
◦ C): (a) BM-CW05, (b) BM-CW05-L10, (c) BM-CW10, (d) BM-CW10-L10,
(−180°C):
temperature (−180
temperature (a) BM-CW05, (b) BM-CW05-L10, (c) BM-CW10, (d) BM-CW10-L10, (e) BM-
(e) BM-CW30,
CW30, and (f) BM-CW30-L10.
and (f) BM-CW30-L10.
Metals 2018, 8, 932 12 of 15
Metals 2018, 8, x FOR PEER REVIEW 12 of 15

3.6.
3.6. Application
Application of
of aa Surface-Cracking
Surface-Cracking Technique
Techniquein
inWeld
WeldMetal
Metal
From
From thethe results
results of
of the
the experiments,
experiments, the the surface-cracking
surface-cracking technique
technique seems
seems to to be
be effective
effective on on
some brittle materials rather than the materials with fully
some brittle materials rather than the materials with fully ductile properties. ductile properties. In particular, it is very
it is very
important
important to to improve
improve the the mechanical
mechanical properties
properties of of the
the weld
weld metal
metal because
because thethe weld
weld metal
metal is is more
more
brittle
brittlethan
thanthe thebase
basemetal.
metal.Therefore,
Therefore, we applied
we applied the surface-cracking technique
the surface-cracking to improve
technique the impact
to improve the
toughness of weld metal. The absorbed energy vs. test temperature
impact toughness of weld metal. The absorbed energy vs. test temperature curves for welded curves for welded specimens
with surface-cracks
specimens is shown in is
with surface-cracks Figure
shown 14.inThe absorbed
Figure 14. The energy of welded
absorbed energyspecimens
of weldedhad a relatively
specimens had
lower valuelower
a relatively compared valuetocompared
the as-received specimen. After
to the as-received a surface-cracking
specimen. process, the
After a surface-cracking absorbed
process, the
energy increased through the effect of surface-cracks at all temperature
absorbed energy increased through the effect of surface-cracks at all temperature regions. As the regions. As the number of
surface-cracks increased from
number of surface-cracks 0 lines tofrom
increased 10 lines, the absorbed
0 lines to 10 lines,energy
the significantly
absorbed energy increased. Similar
significantly
to the results of the cold-worked specimen, the effect of enhanced toughness
increased. Similar to the results of the cold-worked specimen, the effect of enhanced toughness in in welded specimens
with
weldedsurface-cracks
specimens happened at all temperature
with surface-cracks happened regions.
at allIttemperature
was clear that this effect
regions. occurred
It was clear in thatbrittle
this
conditions such in
effect occurred asbrittle
low temperatures,
conditions such cold-worked steel, and weld
as low temperatures, metal.
cold-worked steel, and weld metal.
This
This surface-cracking
surface-cracking technique
technique has enormous
has enormous potential for improving
potential the mechanical
for improving properties
the mechanical
of structureofmaterials.
properties structureFor example,
materials. Forthis technique
example, thisistechnique
also applicable
is alsotoapplicable
corner areas of rectangular
to corner areas of
structures.
rectangularThe rectangular
structures. The structure
rectangular hasstructure
a high risk hasofa fracture
high riskdue to the concentration
of fracture of stress on
due to the concentration
the corner
of stress onareas. It is possible
the corner areas. It to improve to
is possible the toughness
improve by inducing
the toughness bysurface-cracks at the corner
inducing surface-cracks of
at the
rectangular structures.structures.
corner of rectangular We can also Wecontrol
can also the mechanical
control propertiesproperties
the mechanical with this with
technique because
this technique
they are dependent on a cold-working level and surface-cracks. The application
because they are dependent on a cold-working level and surface-cracks. The application of this of this technique to
industrial
technique products
to industrialis designed
productstoischange
designed theirtophysical
change theirproperties andproperties
physical thus improving
and thus theimproving
products’
toughness,
the products’ resistance,
toughness, performance, and durability.
resistance, performance, andThis may offer
durability. Thismany
may benefits
offer many to the optimized
benefits to the
design of high-strength ductile metallic materials in the
optimized design of high-strength ductile metallic materials in the future. future.

Figure
Figure 14.
14. The
The absorbed
absorbed energy
energy vs. test temperature curves for
temperature curves for welded
weldedspecimens
specimenswith
withsurface-cracks.
surface-cracks.

4.
4. Conclusions
Conclusions
In this study,
In this study,wewehavehave developed
developed a new
a new technique
technique usingusing a cold-working
a cold-working processprocess and
and surface-
surface-cracking
cracking process process to increase
to increase the strength
the strength and toughness
and toughness of stainless
of stainless steels steels
at theatsame
the same
time. time.
This
This surface-cracking technique has an enormous potential for improving the mechanical
surface-cracking technique has an enormous potential for improving the mechanical properties of properties
of structure
structure materials.
materials. WeWe cancan
alsoalso control
control the the mechanical
mechanical properties
properties withwith
this this technique
technique because
because they
they are dependent on cold-working levels and surface-cracks. The application
are dependent on cold-working levels and surface-cracks. The application of this technology in of this technology
in industrial
industrial products
products is isdesigned
designedtotochange
changetheir
their mechanical
mechanical properties
properties andand thus
thus improving
improving the the
products’ toughness, strength, and integrity. This may offer many benefits in the optimized
products’ toughness, strength, and integrity. This may offer many benefits in the optimized design design
of
of high-strength
high-strength ductile
ductile metallic
metallic materials
materials inin the
the future.
future. The
The main
main results
results obtained
obtained inin this
this study
study are
are
as follows:
as follows:
Metals 2018, 8, 932 13 of 15

1. After a cold-working process, the microstructure was changed from austenite single phase to
dual phases which consisted of austenite and martensite. The tensile strength and hardness
increased with an increase in the cold-working level. The phase transformation from austenite
to martensite and the increase in dislocations by plastic deformation led to the strengthening of
cold-worked STS304 steels.
2. The specimen with surface-cracks had a higher absorbed energy compared to the as-received
specimen without surface-cracks at low temperature regions (below −60 ◦ C). The dissipation
of the crack propagation energy with surface-cracks enhanced the impact toughness, showing a
ductile fracture mode even in the cryogenic temperature region.
3. The absorbed energy of cold-worked steels decreased with a cold-working level. Comparing
the surface-cracking effect of specimens with the same cold-working level, the absorbed energy
of specimens with surface-cracks was two times higher than that of the specimen without
surface-cracks. In particular, the strength and toughness were simultaneously increased at 5%
cold-worked specimens with surface-cracks. The absorbed energy of the welded specimen had a
relatively lower value compared to the as-received specimen. After a surface-cracking process,
the absorbed energy was increased by effect of a surface-cracking process. Similar to the result of
the cold-worked specimen, toughening by a surface-cracking process in the welded specimen
happened in all temperature regions.

Author Contributions: K.K. and B.J.K. conceived and designed the experiments; K.K. and M.P. performed the
experiments; J.J., H.C.K., H.-S.M., D.-H.L., J.B.J., H.K., S.-H.K., and B.J.K. analyzed and discussed the data;
K.K. and B.J.K. wrote the paper.
Funding: This study was supported by the R&D Program of the Korea Institute of Industrial Technology
(KITECH) as “Fundamental research and development on three-dimensional nano-porous catalysts and gas sensor
for hydrogen production and detection” (KITECH EO-18-0022).
Conflicts of Interest: The authors declare no conflict of interest.

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