metals

Article
Effect of Low-Temperature Sensitization on
Hydrogen Embrittlement of 301 Stainless Steel
Chieh Yu 1, , Ren-Kae Shiue 1 , Chun Chen 1 and Leu-Wen Tsay 2, *
1 Department of Materials Science and Engineering, National Taiwan University, Taipei 106, Taiwan;
d02527001@ntu.edu.tw (C.Y.); rkshiue@ntu.edu.tw (R.-K.S.); gchen@ntu.edu.tw (C.C.)
2 Institute of Materials Engineering, National Taiwan Ocean University, Keelung 20224, Taiwan
* Correspondence: b0186@mail.ntou.edu.tw; Tel.: +886-2-2462-5324
Current Address: National Chung-Shan Institute of Science and Technology, Materials & Electro-Optics
Research Division, Lung-Tan, Tao-Yuan 325, Taiwan.

Academic Editor: Robert Tuttle

Received: 7 January 2017; Accepted: 10 February 2017; Published: 15 February 2017

Abstract: The effect of metastable austenite on the hydrogen embrittlement (HE) of cold-rolled
(30% reduction in thickness) 301 stainless steel (SS) was investigated. Cold-rolled (CR) specimens
were hydrogen-charged in an autoclave at 300 or 450 C under a pressure of 10 MPa for 160 h
before tensile tests. Both ordinary and notched tensile tests were performed in air to measure the
tensile properties of the non-charged and charged specimens. The results indicated that cold rolling
caused the transformation of austenite into 0 and -martensite in the 301 SS. Aging at 450 C
enhanced the precipitation of M23 C6 carbides, G, and phases in the cold-rolled specimen. In
addition, the formation of 0 martensite and M23 C6 carbides along the grain boundaries increased
the HE susceptibility and low-temperature sensitization of the 450 C-aged 301 SS. In contrast,
the grain boundary 0 -martensite and M23 C6 carbides were not observed in the as-rolled and
300 C-aged specimens.

Keywords: stainless steel; hydrogen embrittlement; hydrogen charging; G and phases;

0 martensite

1. Introduction
Austenitic stainless steels (SSs) have been extensively used in industrial applications due to
their good combination of corrosion resistance and mechanical properties. Metastable austenitic
SSs may undergo phase transformation from austenite () into ferromagnetic 0 -martensite during
plastic deformation [15]. The induced martensite during tensile tests at room temperature enhances
the elongation to fracture, hardness, and tensile strength [5]. However, the induced martensite
increases the susceptibility of austenitic stainless steels to hydrogen embrittlement (HE) [28].
In hydrogen-containing environments, the more austenite transforms into martensite, the more
ductility loss of the material occurs [6]. Hydrogen suppresses the transformation of austenite to
martensite, leading to hydrogen softening and localized brittle fracture [5]. Moreover, the suppressed
formation of 0 -martensite in the highly strained region of a 304L specimen at 80 C accounts for
its lowered HE susceptibility [7]. It has been reported that strain-induced 0 -martensite acts as a
hydrogen diffusion highway in hydrogen-charged 304 SS [8], resulting in an increased hydrogen
concentration at the crack tip and accelerated crack growth.
Austenitic stainless steels are susceptible to stress corrosion cracking (SCC) in chloride-containing
solutions [915]. In MgCl2 solution, the mechanism of environment-induced cracking of austenitic
stainless steels can be either SCC or HE, depending on the test temperature [10,11]. A suitable
amount of cold work can lower the SCC susceptibility of austenitic stainless steels, whereas excessive

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Metals 2017, 7, 58 2 of 12

cold working reverses that trend [16,17]. The machined 304L SS showed a marked increase in SCC
susceptibility as compared with the solution-annealed, unmachined, and cold worked samples [18,19].
Unlike martensite-free 304 SS, 304 SS with machining-induced martensite is greatly embrittled and
undergoes premature failure in 40 MPa hydrogen [20].
As austenitic stainless steels are heated in the temperature range between 500 C and 850 C,
chromium carbides form along the grain boundary, leaving an adjacent chromium depletion zone. This
phenomenon is called sensitization and it is responsible for intergranular corrosion or intergranular
SCC (IGSCC) [2124]. Cold-working austenitic stainless steels accelerates carbide precipitation, even
in a Ti-stabilized (AISI 321) SS [24]. Cathodic hydrogen-charging greatly reduces the ductility of
tensile specimens and decreases the time-to-failure of 304L SS and 308L weld metals under constant
load tests, especially for the sensitized 304L (650 C/24 h aging) [22]. Furthermore, the nucleation of
tiny carbides in many austenitic SSs is enhanced by welding, thermo-mechanical processing, or slow
cooling from the solution-annealed temperature. Such thermo or thermo-mechanical processes might
not immediately induce IGSCC of the alloys. The number of carbide precipitates remains unchanged,
but they grow in size during subsequent long-term service below 500 C. Sensitization of austenitic SSs
at temperatures below the classic sensitization range (500 C800 C) is referred to as low-temperature
sensitization (LTS).
Cold deformation increases the degree of 304 SS sensitization up to 65 times that of undeformed
304 SS tested at 500 C [25]. In a previous study, 304 SS welds exposed to a temperature of
450 C for 6600 h suffered from IGSCC due to the presence of (Fe,Cr)23 C6 carbides along grain
boundaries [26]. Cold working of the steel increases the sensitization kinetics of austenitic SSs by up
to 15%, while further cold working shows less effect on sensitization [23]. The induced martensite
in cold-worked 304 [27] or 304L [28] SSs causes low-temperature sensitization at 380 C [27] and
500 C [28], thereby increasing the SCC susceptibility in a BWR (boiling water reactor) simulated
environment [28]. Furthermore, sensitization causes 0 -martensite transformation preferentially along
the grain boundaries of 304 and 316 SSs, which provides a high diffusivity path of hydrogen to the
crack tip [29] and enhances the intergranular fracture and HE susceptibility of the steel [29].
In this study, cold-rolled 301 SS was hydrogen-charged in an autoclave at 300 C or 450 C
at the pressure of 10 MPa for 160 h before straining. The effects of low-temperature sensitization
during aging/hydrogen-charging at 300 C or 450 C on the microstructure were investigated. The HE
susceptibility of various specimens was correlated with the corresponding microstructures, particularly
the induced martensite and fine precipitates in the specimens.

2. Experimental Procedures
The chemical composition of the AISI 301 SS used in this study was 16.71 Cr, 6.89 Ni, 0.08 C,
1.16 Mn, 0.54 Si, 0.02 P, 0.003 S, and the balance Fe in wt %. The 301 SS in the plate form with a thickness
of 4.5 mm was solution-annealed at 1050 C for 30 min and had a hardness of Hv 176. Cold rolling of
the 301 SS plate with 30 % in thickness reduction was performed at room temperature, and designated
as CR (cold-rolled) specimen. For comparison, CR specimens were aged at 300 C or 450 C for 160 h,
and these specimens were respectively designated as CR-300 and CR-450.
Figure 1 shows the dimensions of the double-edge notched tensile and standard tensile specimens,
which had a thickness of 3 mm. Cold-rolled specimens were hydrogen-charged in an autoclave at
300 C or 450 C at a pressure of 10 MPa for 160 h before straining. They were designated as CR-300H
and CR-450H, respectively. Standard tensile specimens, according to ASTM E8 specification with a
gauge length of 25 mm, were wire-cut directly from the cold-rolled plates along the rolling direction.
Ordinary tensile tests were carried out at a strain rate of 6 104 s1 (crosshead displacement rate of
0.9 mm/min) in laboratory air to determine the tensile properties of the non-hydrogen-charged
specimens. Notched tensile tests were performed to evaluate the HE susceptibility of the
hydrogen-charged specimens at a crosshead displacement rate of 0.72 mm/min at room temperature.
Metals 2017, 7, 58 3 of 12
Metals 2017, 7, 58 3 of 12

Figure
Figure 1.
1. Schematic
Schematic dimensions
dimensions of
of (a)
(a) aa double-edge
double-edge notched
notched specimen
specimen and
and (b)
(b) aa standard
standard tensile
tensile
specimen. (RD:
(RD: Rolling
Rolling Direction).
Direction).

A Fischer MP30 ferritescope (Windsor, CT, USA) can measure the ferrite contents precisely in
A Fischer MP30 ferritescope (Windsor, CT, USA) can measure the ferrite contents precisely in
austenitic and duplex SSs. The ferritescope was used in this study to determine the amounts of
austenitic and duplex SSs. The ferritescope was used in this study to determine the amounts of
strain-induced -martensite in all specimens [30,31]. The hydrogen-charged samples (CR-300H and
strain-induced 0 -martensite in all specimens [30,31]. The hydrogen-charged samples (CR-300H and
CR-450H) with the dimensions of 1 1 1 cm3 3were ground by No. 2000 SiC paper before cleaning.
CR-450H) with the dimensions of 1 1 1 cm were ground by No. 2000 SiC paper before cleaning.
The hydrogen contents of the charged samples (CR-300H and CR-450H) were measured by using the
The hydrogen contents of the charged samples (CR-300H and CR-450H) were measured by using the
LECO-TCH 600 (Saint Joseph, MI, USA). After hydrogen-charging, they were melted in a crucible.
LECO-TCH 600 (Saint Joseph, MI, USA). After hydrogen-charging, they were melted in a crucible.
The amounts of H and O were calculated from the H2O, CO, and CO2 mixture. Fractographs of each
The amounts of H and O were calculated from the H2 O, CO, and CO2 mixture. Fractographs of each
specimen after tensile straining were inspected with a NOVA-450 scanning electron microscope
specimen after tensile straining were inspected with a NOVA-450 scanning electron microscope (SEM,
(SEM, Hillsboro, OR, USA). Selected specimens were inspected by using a JEOL 2000EX
Hillsboro, OR, USA). Selected specimens were inspected by using a JEOL 2000EX transmission electron
transmission electron microscope (TEM, Akishima, Japan). A high resolution TEM (HRTEM), FEI
microscope (TEM, Akishima, Japan). A high resolution TEM (HRTEM), FEI Tecnai G2 F20 (Hillsboro,
Tecnai G2 F20 (Hillsboro, OR, USA), was applied to inspect the nano-sized precipitates in the
OR, USA), was applied to inspect the nano-sized precipitates in the specimen.
specimen.
3. Results
3. Results
3.1. Microstructural Observation
3.1. Microstructural Observation
Figure 2 shows optical metallographs of cold-rolled specimens with different aging conditions.
FigureFigure
2a is2ashows optical
composite metallographs
photograph of theofCR
cold-rolled
specimenspecimens
revealing with different aging along
the microstructures conditions.
three
Figure 2a is a composite
perpendicular directions.photograph of the CR
No severe texture wasspecimen
observed revealing
in the CR thespecimen
microstructures
after 30% along three
thickness
perpendicular
reduction. Thedirections.
CR specimen No contained
severe texture was observed
basket-weaved slip in the CR
bands specimen
within afteraustenite
equiaxial 30% thickness
grains.
reduction.
In the case ofThe
theCR specimen
specimens contained
aged basket-weaved
at 300 (CR-300)
and 450 slip bands within
C (CR-450), equiaxial
slip bands couldaustenite grains.
be still observed
In the case
clearly, of theinspecimens
as shown Figure 2b,c. aged
The at 300 (CR-300)
ferritescope was andused450 C (CR-450),
to determine slip bands
the amount could be still
of strain-induced
0
observed
martensiteclearly, as shown
formed in the in Figure
tested 2b,c. The The
specimens. ferritescope was used
ferrite contents to determine
of the CR, CR-300, theand
amount
CR-450of
strain-induced
specimens were 26%,
martensite
26%, andformed29%,inrespectively.
the tested specimens.
It is well Theknownferrite
thatcontents
heatingofstrain-induced
the CR, CR-300, 0
and CR-450
martensite to specimens were
an appropriate 26%, 26%,will
temperature and 29%,
cause respectively.
it to It is wellleading
revert into austenite, knownto that heating
a decrease in
strain-induced
ferrite content. martensite
It was deduced tothat
an appropriate temperature
increased amount 0 will causeinitthe
of martensite to CR-450
revert into austenite,
specimen was
leading
associatedto awith
decrease in ferrite
a specific phasecontent. It was deduced
transformation that increased amount of martensite in the
in the specimen.
CR-450 specimen was associated with a specific phase transformation in the specimen.
Metals 2017, 7, 58 4 of 12
Metals 2017, 7, 58 4 of 12

(a)

(b) (c)

Figure 2.2. Optical

Figure Opticalmetallographs
metallographsof:of:(a)(a)three
three mutually
mutually perpendicular
perpendicular planes
planes of CR,
of the the CR, (b) CR-300,
(b) CR-300, and
and (c) CR-450 specimens.
(c) CR-450 specimens.

3.2. Mechanical Properties

3.2. Mechanical Properties
Table 1 lists the mechanical properties of the test specimens. The 30% cold rolling obviously
Table 1 lists the mechanical properties of the test specimens. The 30% cold rolling obviously
increased the surface hardness of CR specimen to Hv 455, as compared with the Hv 176 of the
increased the surface hardness of CR specimen to Hv 455, as compared with the Hv 176 of the annealed
annealed 301 SS. Dislocation recovery during aging at 300 C was expected to be responsible for the
301 SS. Dislocation recovery during aging at 300 C was expected to be responsible for the slight
slight decrease in surface hardness of CR-300 specimen to Hv 445. The surface hardness of CR-450
decrease in surface hardness of CR-300 specimen to Hv 445. The surface hardness of CR-450 specimen
specimen further reduced to Hv 414 due to the overage at 450 C. The results of ordinary tensile tests
further reduced to Hv 414 due to the overage at 450 C. The results of ordinary tensile tests revealed
revealed that all three tested specimens had the same elongation of 24%. The ordinary tensile
that all three tested specimens had the same elongation of 24%. The ordinary tensile strengths of the
strengths of the CR and CR-300 specimens were similar. However, the YS and UTS of the CR-450
CR and CR-300 specimens were similar. However, the YS and UTS of the CR-450 specimen were lower
specimen were lower than those of the CR and CR-300 ones.
than those of the CR and CR-300 ones.
Table 1.
Table 1. Mechanical
Mechanical properties
properties of
of tested
tested specimens
specimens with
with 30%
30% reduction
reductionin
inthickness.
thickness.

YS a UTS b EL cc Hardness NTS d

Specimen Specimen
YS a (MPa) UTS b (MPa) EL (%) Hardness(Hv) NTS d (MPa)
(MPa) (MPa) (%) (Hv) (MPa)
CR CR1350 1350 15061506 2424 455 4551737 1737
CR-300 e 1400 e 1544 24 445 1743
CR-300 1400 1544 24 445 1743
CR-450 f 1200 1296 24 414 1584
CR-300H g CR-450-
f 1200 - 1296 24 - 414 - 1584 1339
CR-450H h CR-300H - g - - - - - - - 1339 843
CR-450H
a YS: offset yield strength; h
b UTS: - - c - d - 843 e
ultimate tensile strength; EL: elongation; NTS: notched tensile strength; CR-300:
CR specimen
a YS: aged at
offset yield 300 C for
strength; 160 hultimate
b UTS: in vacuum; f CR-450: CR specimen
tensile aged at 450d NTS:
strength; c EL: elongation; C for 160 h in vacuum;
notched tensile
g CR-300H: CR specimen hydrogen-charged at 300 C for 160 h; h CR-450H: CR specimen hydrogen-charged at
strength; e CR-300: CR specimen aged at 300 C for 160 h in vacuum; f CR-450: CR specimen aged at
450 C for 160 h.
450 C for 160 h in vacuum; g CR-300H: CR specimen hydrogen-charged at 300 C for 160 h;
h CR-450H: CR specimen hydrogen-charged at 450 C for 160 h.
Metals 2017, 7, 58 5 of 12
Metals 2017, 7, 58 5 of 12

Notched
Notched tensile
tensile tests
tests were
were performed
performed in in air
air to
to evaluate
evaluate the the notch
notch brittleness
brittleness of of the
the specimens.
specimens.
The NTSs of the CR, CR-300, and CR-450 specimens were 1737, 1743,
The NTSs of the CR, CR-300, and CR-450 specimens were 1737, 1743, and 1584 MPa, respectively. and 1584 MPa, respectively.
The
The NTS
NTS of of the
the CR-450
CR-450 specimen
specimen was was lower
lower than
than those
those of
of the
the CRCR andand CR-300
CR-300 ones.
ones. This
This isis consistent
consistent
with the YS and UTS results for the CR, CR-300, and CR-450 specimens.
with the YS and UTS results for the CR, CR-300, and CR-450 specimens. It is noted that the NTS It is noted that the NTS
was
was
significantly higher than the corresponding UTS for all specimens, indicating that the notched
significantly higher than the corresponding UTS for all specimens, indicating that the notched
specimens
specimens possessed
possessed enough
enough toughness
toughness to to resist
resist localized
localized brittle
brittlefracture
fracturebefore
beforerupture
rupturein inair.
air.
Notched
Notched tensile strengths tested in air versus displacement curves of the non-charged (solid
tensile strengths tested in air versus displacement curves of the non-charged (solid
lines)
lines) and
andhydrogen-charged
hydrogen-charged(dotted (dottedlines)
lines)specimens
specimens areare
shown
shown in Figure
in Figure3. The NTSs
3. The of the
NTSs of CR
theand
CR
CR-300 specimens were similar, but the CR-300 specimen had
and CR-300 specimens were similar, but the CR-300 specimen had a slightly higher notcha slightly higher notch displacement
(notch ductility)
displacement than the
(notch CR one.
ductility) In contrast,
than the CR one. the NTS and notch
In contrast, thedisplacement
NTS and notch of the CR-450 specimen
displacement of the
were
CR-450 obviously
specimen lower
were than those of lower
obviously the CRthan and CR-300
those ofonesthe tested
CR and in air. Subsequently,
CR-300 ones tested agingin the
air.
cold-rolled 301 SS at 450 C was found to deteriorate its notched tensile properties. As shown in
Subsequently, aging the cold-rolled 301 SS at 450 C was found to deteriorate its notched tensile
Figure 3, hydrogen-charging
properties. As shown in Figure caused a significant drop
3, hydrogen-charging in NTSs
caused and notchdrop
a significant displacements
in NTSs and ofnotch
both
the CR-300H and
displacements CR-450H
of both specimens.
the CR-300H andHE was responsible
CR-450H specimens.for HE such
wasa responsible
severe degradation
for such of notch
a severe
tensile properties of the hydrogen-charged specimens. The results
degradation of notch tensile properties of the hydrogen-charged specimens. The results also also indicated that the CR-450H
specimen
indicated wasthat more damaged
the CR-450H by hydrogen-charging
specimen was more damaged than the
by CR-300H one. Agingthan
hydrogen-charging the the
coldCR-300H
worked
specimen at higher temperature was expected to improve its ductility and
one. Aging the cold worked specimen at higher temperature was expected to improve its ductility reduce brittleness, but these
improvements did not occur in the CR-450 specimen. This result would
and reduce brittleness, but these improvements did not occur in the CR-450 specimen. This result be addressed in the later
discussion of the mechanism
would be addressed of deterioration
in the later discussion ofin theCR-450.
mechanism of deterioration in CR-450.

Figure 3.
Figure 3. Notched
Notched tensile
tensile tests
tests of
of non-hydrogen-charged
non-hydrogen-charged (solid
(solid lines)
lines) and
and hydrogen-charged
hydrogen-charged (dash
(dash
lines) specimens.
lines) specimens.

3.3. Fractographic
3.3. Fractographic Examinations
Examinations
The macroscopic
The macroscopicfracture
fracture appearances
appearances of selected
of selected notched
notched tensiletensile specimens
specimens are shownare inshown
Figurein4.
Figure
The 4. The fractographs
fractographs of the CR of andthe CR and
CR-300 CR-300 specimens
specimens were alike,were alike, comprising
comprising extensive
extensive shear shear
fractured
fractured
(SF) regions(SF) regions
(shear lips)(shear
on thelips) onsurfaces
lateral the lateral
andsurfaces andflat
triangular triangular
fracture flat
(FF)fracture (FF) zones
zones ahead of the ahead
notch
fronts, as shown in Figure 4a. A noticeable reduction of the SF regions and an increase in increase
of the notch fronts, as shown in Figure 4a. A noticeable reduction of the SF regions and an in
the size of
the FF
the size of the
zone wereFFobserved
zone were observed
in the CR-450inspecimen
the CR-450 specimen
after aftertensile
the notched the notched tensile
test (Figure 4b).test (Figure
Moreover,
4b). Moreover, the fractograph shown in Figure 4b exhibited lamellar tears and
the fractograph shown in Figure 4b exhibited lamellar tears and many fine secondary cracks. Even many fine secondary
cracks. Even
without without hydrogen-charging,
hydrogen-charging, the CR-450
the CR-450 specimen specimen
showed showed
inherent notchinherent notch
brittleness inbrittleness
comparison in
comparison
with the CR andwithCR-300
the CRspecimens.
and CR-300 specimens.
It is known that hydrogen tends to accumulate and embrittle the elastic-plastic boundaries of
high-strength steels [32], and this embrittlement becomes more severe at the locations of stress
concentration, such as a notch [33,34]. Moreover, a notch can produce a triaxial stress state, and
limits the plastic deformation ahead of the notch tip. The marked decreases in NTSs and notch
displacements of the hydrogen-charged specimens (CR-300H and CR-450H in Figure 3) were
Metals 2017, 7, 58 6 of 12

associated with significant changes in their fractographs as illustrated in Figure 4c,d. In the CR-300H
specimen, most SF zones were replaced by FF regions with parallel secondary cracks (Figure 4c). For
Metals 2017, 7, 58 6 of 12
the CR-450H specimen, the fractured surface was dominated by FF regions (Figure 4d) due to the
high HE susceptibility.

Figure 4. Macro-fracture
Figure appearances
Macro-fracture of (a) of
appearances CR-300, (b) CR-450,
(a) CR-300, (b) (c) CR-300H,
CR-450, (c) and (d) CR-450H
CR-300H, and
(d) CR-450H specimens.
specimens.

ItFailure analyses
is known of all fractured
that hydrogen tends tosurfaces after tensile
accumulate tests were
and embrittle the performed using
elastic-plastic an SEM.
boundaries
Ductile
of dimple fracture
high-strength was
steels [32], andobserved in all ordinary
this embrittlement becomestensile specimens
more severe at(not
the shown
locationshere). SEM
of stress
fractographs of selected specimens after notched tensile tests are presented in
concentration, such as a notch [33,34]. Moreover, a notch can produce a triaxial stress state, and Figure 5. The fracture
modesthe
limits of the CR-300
plastic and CR-450
deformation specimens
ahead differed
of the notch tip.slightly. In the CR-300
The marked decreasesspecimen,
in NTSs predominant
and notch
fine shallow dimples mixed with sparsely flat cleavage-like fracture were
displacements of the hydrogen-charged specimens (CR-300H and CR-450H in Figure 3) were associatedobserved within the FF
zones ahead of notch front (Figure 5a). In contrast, mainly cleavage fracture with
with significant changes in their fractographs as illustrated in Figure 4c,d. In the CR-300H specimen, secondary cracks
alongSF
most austenite grain replaced
zones were boundaries by was found ahead
FF regions with of the notch
parallel front of the
secondary CR-450
cracks specimen
(Figure (Figure
4c). For the
5b), indicating the brittle nature of the sample. The CR-450 specimen,
CR-450H specimen, the fractured surface was dominated by FF regions (Figure 4d) due to the high even without
hydrogen-charging,
HE susceptibility. was likely to suffer intergranular fracture under strain. Regarding the
hydrogen-charged
Failure analysesspecimens, extensive
of all fractured surfacescleavage-like
after tensilefracture
tests weretogether withusing
performed numerous
an SEM.secondary
Ductile
cracks was observed in the CR-300H specimen (Figure 5c), while the CR-450
dimple fracture was observed in all ordinary tensile specimens (not shown here). SEM fractographs specimen mainly
exhibited
of selectedintergranular
specimens after fracture
notched(Figure 5d).
tensile tests are presented in Figure 5. The fracture modes of the
CR-300 and CR-450 specimens differed slightly. In the CR-300 specimen, predominant fine shallow
dimples mixed with sparsely flat cleavage-like fracture were observed within the FF zones ahead of
notch front (Figure 5a). In contrast, mainly cleavage fracture with secondary cracks along austenite
grain boundaries was found ahead of the notch front of the CR-450 specimen (Figure 5b), indicating
the brittle nature of the sample. The CR-450 specimen, even without hydrogen-charging, was likely
to suffer intergranular fracture under strain. Regarding the hydrogen-charged specimens, extensive
cleavage-like fracture together with numerous secondary cracks was observed in the CR-300H
specimen (Figure 5c), while the CR-450 specimen mainly exhibited intergranular fracture (Figure 5d).

Figure 5. Cont.
along austenite grain boundaries was found ahead of the notch front of the CR-450 specimen (Figure
5b), indicating the brittle nature of the sample. The CR-450 specimen, even without
hydrogen-charging, was likely to suffer intergranular fracture under strain. Regarding the
hydrogen-charged specimens, extensive cleavage-like fracture together with numerous secondary
cracks was observed in the CR-300H specimen (Figure 5c), while the CR-450 specimen mainly
Metals 2017, 7, 58 7 of 12
exhibited intergranular fracture (Figure 5d).

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Figure 5. Cont.

Figure 5. SEM fractographs of (a) CR-300, (b) CR-450, (c) CR-300H, and (d) CR-450H specimens after
Figure 5.
notched
notched tensile
tensile test.
test.

3.4. TEM Examinations

Figure 6 displays
displays detailed
detailed TEM
TEM micrographs
micrographs of of the
the CR
CR specimen.
specimen. There were three distinct
structures-martensite, 0
structures-martensite,-martensite, andaustenitein
-martensite, and austenitein the
the CRCR specimen.
specimen. TheThe microstructure
microstructure of
of the
the specimen
CR CR specimen waswas primarily
primarily comprised
comprised of parallel
of parallel strips
strips of -martensite
of -martensite (hcp)
(hcp) in austenite
in the the austenite (,
(, fcc)
fcc) matrix,
matrix, as illustrated
as illustrated in Figure
in Figure 6a.-martensite
6a. The The -martensite
formed formed
in slipin slip bands
bands due to due to the
the 30% 30%
cold cold
rolling
rolling
of the 301of SS.
theThe 0
301SS. The -martensite
-martensite (bcc)been
(bcc) had also had found
also been found
mainly mainly
at the at the intersections
intersections of -martensiteof
-martensite
strips. Similarstrips.
resultsSimilar results were
were obtained obtained
in prior in the
study of prior
SCCstudy of the SCC
of cold-rolled of cold-rolled
304L 304L SS
SS [4,12], consistent
[4,12],the
with consistent
location of 0 -martensite,
with the location asof shown
-martensite, as6b.
in Figure shown in Figure 6b.

Figure 6.
Figure 6. TEM
TEM micrographs
micrographs of of the
the CR
CR specimen
specimen illustrating
illustrating (a)
(a) -martensite
-martensite strips
strips in
in the
the austenite
austenite
matrix, (b) -martensite
0 at the intersections of -martensite strips.
matrix, (b) -martensite at the intersections of -martensite strips.

In the CR-450 specimen, further aging at 450 C for 160 h enhanced the transformation of
In the CR-450 specimen, further aging at 450 C for 160 h enhanced the transformation of
metastable austenite into -martensite and the precipitation of M23 23C66 carbides along the grain
metastable austenite into 0 -martensite and the precipitation of M23 C6 carbides along the grain
boundaries, as displayed in Figure 7. In the CR and CR-300 specimens, the grain boundary
boundaries, as displayed in Figure 7. In the CR and CR-300 specimens, the grain boundary
-martensite and M23 23C66 carbides were not observed. Due to the presence of fresh grain boundary
0 -martensite and M23 C6 carbides were not observed. Due to the presence of fresh grain boundary
-martensite, the ferrite contents of the CR-450 specimen were higher than those of the CR and
0 -martensite, the ferrite contents of the CR-450 specimen were higher than those of the CR and
CR-300 specimens. Both the precipitation of M23 23C66 carbides and increased -martensite along the
grain boundaries resulted in increasing HE susceptibility of the CR-450H specimen, as compared
with the CR-300H specimens. It was obvious that cold rolling the 301 SS induced partial austenite
transformation into - and -martensite. The subsequent aging at 450 C promoted the formation of
grain boundary -martensite and M23 23C66 carbides, which were responsible for the low-temperature
Metals 2017, 7, 58 8 of 12

CR-300 specimens. Both the precipitation of M23 C6 carbides and increased 0 -martensite along the
grain boundaries resulted in increasing HE susceptibility of the CR-450H specimen, as compared
with the CR-300H specimens. It was obvious that cold rolling the 301 SS induced partial austenite
transformation into 0 - and -martensite. The subsequent aging at 450 C promoted the formation of
grain boundary 0 -martensite and M23 C6 carbides, which were responsible for the low-temperature
Metals 2017, 7, 58 8 of 12
sensitization of the SS.

Figure 7. TEM images of the CR-450 specimen: (a) bright field image, (b) dark field image of carbides
using (111) diffraction spot, (c) dark field image of 0
martensite using (101) spot, (d) selected area
diffraction pattern with two identified structures.
structures.

Figure 88 shows
Figure shows TEMTEM images
images of of the
the G
G and
and phases
phases inin the
theCR-450
CR-450specimen.
specimen. Nano-sized
Nano-sized
precipitates, G and phases, were found in the martensite
0 of the CR-450
precipitates, G and phases, were found in the martensite of the CR-450 specimen, as specimen, as shown
shownin
Figure
in 8ac.
Figure 8ac.TheTheaverage
averagesize of of
size thethe
G Gphase
phaseprecipitates
precipitateswas
wasgreater
greaterthan
thanthat
that of
of the
the phase
phase
precipitates. The lattice image was transformed into a diffraction pattern by fast Fourier
precipitates. The lattice image was transformed into a diffraction pattern by fast Fourier transform transform
(FFT) for
(FFT) for identification
identification of of the
the crystal
crystal structure
structure ofof nano-sized
nano-sized precipitates
precipitates byby high
high resolution
resolution TEM.
TEM.
Figure 8b
Figure 8bisisa lattice
a lattice image
image of G
of the the G phase
phase formedformed
in the in the ' with
' matrix matrix withzone
a [100] a [100]
axis.zone axis. A
A precipitate
precipitate
in in thewith
the 0 matrix matrix
a [013]with
zonea axis
[013]iszone
shownaxis
inisFigure
shown in Figure 8d.
8d.
Metals 2017, 7, 58 9 of 12
Metals 2017, 7, 58 9 of 12

Figure
Figure 8. TEM images
8. TEM images and
and high
high resolution
resolution lattice
lattice images
images with
with fast
fast Fourier
Fourier transform
transform diffraction
diffraction
patterns
patterns of
of the
the CR-450
CR-450 specimen:
specimen: (a,b)
(a,b) G
G phase;
phase; and
and (c,d)
(c,d) phase.
phase.

4. Discussion
In general,
general,anan increase
increasein annealing temperature
in annealing reducesreduces
temperature the strain-hardening effect of cold-rolled
the strain-hardening effect of
steels. Annealing
cold-rolled steels. treatment
Annealingcan improve
treatment canthe resistance
improve the of work-hardened
resistance steel to HE.
of work-hardened As to
steel shown
HE. As in
Figure
shown 6,incoldFigurework 6, enhanced
cold workthe formation
enhanced theofformation
- and -martensite in the metastable
of - and -martensite in theaustenitic
metastable SS.
Moreover,
austenitic metastable
SS. Moreover, austenitic SSs undergo
metastable traditional
austenitic SSs undergosensitization whensensitization
traditional heated abovewhen 500 heated
C, and
low-temperature
above 500 C, andsensitization
low-temperature occurssensitization
below 500 occurs C, if the cold 500
below work C,isifapplied.
the coldThe work formation
is applied.of
induced 0 -martensite is responsible for its easy sensitization. In this work, aging the cold-rolled
The formation of induced -martensite is responsible for its easy sensitization. In this work, aging
301 SS at 450 C301
the cold-rolled (CR-450)
SS at 450assisted the formation
C (CR-450) assistedofthegrain boundary
formation 0 -martensite
of grain boundary and M23 C6 carbides.
-martensite and
In
M23contrast,
C6 carbides. grain
In boundary
contrast, grain boundaryand
-martensite M23 C6 carbides
-martensite and Mwere not observed
23C6 carbides were notin the CR and
observed in
CR-300 specimens.
the CR and CR-300 specimens.
As illustrated
illustratedininTableTable1,1,both
bothUTSUTSand YS YS
and of the CR-300
of the specimen
CR-300 specimenwerewere
slightly higherhigher
slightly than those
than
of the of
those CRtheone. CRInone.
contrast, UTS and
In contrast, YS and
UTS of theYSCR-450
of the specimen were obviously
CR-450 specimen lower than
were obviously those
lower of
than
CR and
those ofCR-300
CR andones. CR-300 Moreover, all specimens
ones. Moreover, showed equivalent
all specimens tensile elongation
showed equivalent tested in air.
tensile elongation The
tested
results indicated
in air. The resultsincreasing
indicatedthe annealing
increasing thetemperature to 450 C didtonot
annealing temperature 450improve
C did notthe ductility
improve but the
caused
ductilitya decline
but caused in strength
a decline of in
thestrength
cold worked
of the301coldSS.worked
The results of notched
301 SS. The resultstensile tests in air
of notched also
tensile
revealed
tests in airthat therevealed
also NTS of CR-450
that thespecimen was lower
NTS of CR-450 than those
specimen was of the others.
lower As shown
than those of theinothers.
FigureAs 4,
the CR-450
shown specimen
in Figure comprised
4, the of extensive
CR-450 specimen flat fracture
comprised region (Figure
of extensive 4b), in contrast,
flat fracture shear fracture
region (Figure 4b), in
dominated
contrast, shear the fractographs
fracture dominated of CR andthe CR-300 specimens
fractographs of CR(Figure 4a). It specimens
and CR-300 demonstrated the fact
(Figure 4a). ofIt
high notch brittleness
demonstrated the fact of of the
highCR-450
notch specimen,
brittleness and
of thecould be related
CR-450 to the
specimen, brittle
and could microstructures
be related to the in
brittle microstructures in the specimen. SEM fractographs of the CR-450 specimen after the notched
tensile test in air showed cleavage-like fracture along with intergranular fracture (Figure 5b), which
Metals 2017, 7, 58 10 of 12

the specimen. SEM fractographs of the CR-450 specimen after the notched tensile test in air showed
cleavage-like fracture along with intergranular fracture (Figure 5b), which could be associated with
the formation of grain boundary 0 -martensite and M23 C6 carbides, as shown in Figure 7. Without the
presence of brittle microstructures along grain boundaries, the notched fracture appearance of the CR
and CR-300 specimens showed predominantly shallow dimple fracture (Figure 5a).
It was reported that the HE susceptibility of the austenitic SSs is affected by the
compositions [35,36] and prestrained level of the SS [37,38]. Dynamic interactions between hydrogen
and the induced martensite play important roles in the HE of the hydrogen-charged 304 SS [37].
The hydrogen enhances the formation of 0 -martensite, which facilitates HE and dominates the
fracture process of the metastable austenitic SS [7]. Moreover, the hydrogen source influences the
location of crack initiation and propagation in austenitic SSs. An external hydrogen source promotes
crack initiation and propagation at the surface. Similar to surface cracks, the propagation of internal
cracks is accelerated by the presence of internal hydrogen in the 304 and 316 SSs [35].
In Table 1, both CR-300H and CR-450H specimens were highly susceptible to internal HE,
especially for the CR-450H one. It was deduced that high sensitivity to HE of the cold worked
301 SS could be attributed to its low austenite stability under straining. The CR-450H specimen
suffered from a greater loss of ductility than the CR-300H specimen, as displayed in Figure 3. Both
macro- and micro-fractographs, as shown in Figures 4 and 5, also confirmed that the CR-450H specimen
was more susceptible to internal HE than the CR-300H specimen. High extent of intergranular fracture
in the CR-450H specimen was associated with the brittle characteristics of grain boundaries.
Nano-sized G and particles were observed in 0 -martensite of CR-450 specimen (Figure 8).
The precipitation of G phase in the ferrite matrix has also been reported in the duplex SS after
prolonged aging above 350 C [39]. The precipitation of nano-sized G and phases further
strengthened the interiors of the grains of the CR-450 sample. The strengthening of the grain interior
by nano-sized precipitates highlighted the weakness of the embrittled grain boundaries and favored
crack propagation therein. Actually, hydrogen-charging caused more hydrogen to diffuse into the
specimen at 450 C than that at 300 C. The hydrogen concentrations of the CR-300H and CR-450H
were 12 and 20 ppm, respectively. A high hydrogen concentration is usually accompanied by high HE
susceptibility. Both the deteriorated microstructure and the high hydrogen content accounted for the
high HE susceptibility and extensive intergranular fracture of the CR-450H specimen.

5. Conclusions
The effects of cold rolling and subsequent hydrogen-charging at 300 C or 450 C for 160 h
on the microstructure, tensile properties, and HE susceptibility of 301 SS were investigated. Cold
rolling caused -martensite to form in parallel strips of the slip bands, and 0 -martensite was found
mainly at the intersections of -martensite. Hydrogen-charging at 300 C and 450 C led to severe
HE of the cold-rolled 301 SS, particularly in the 450 C charged specimens. In specimens that were
not hydrogen-charged, the notched tensile fracture of the 450 C-aged one showed brittle fracture
appearance, which comprised of cleavage-like fracture together with intergranular separations. In the
CR-450 specimen, 0 -martensite and M23 C6 carbides were formed along the grain boundary. Because
of this fresh grain boundary of 0 -martensite, the ferrite contents of the CR-450 specimen were higher
than those of the CR and CR-300 specimens. Moreover, very fine precipitates including the G and
phases were found in the 0 -martensite. The formation of grain boundary 0 -martensite and M23 C6
carbides together with nano-sized precipitates in the 0 -martensite were responsible for the high HE
susceptibility and low-temperature sensitization of the CR-450 specimen. In contrast, those of grain
boundary precipitates and nano-sized phases were not observed in the CR and CR-300 specimens.

Acknowledgments: The authors gratefully acknowledge the partial financial support of this research by the
National Science Council, Republic of China, Taiwan.
 Metals 2017, 7, 58 11 of 12

Author Contributions: L.W. Tsay and R.K. Shiue designed and planned the experiment. C. Chen contributed to
the discussion of the results. C. Yu performed the tests and TEM examinations. All co-authors contributed to the
manuscript
Metals
Metals 2017,
2017, proof
7, 7,
58 58 and submissions. 1111
ofof
1212
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts
Conflicts ofof Interest:The
Interest: The authors
authors declare
declare nono conflict
conflict ofof interest.
interest.
References
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Metals 2017,7,
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