metals

Article
Effect of Micro-Segregation on Impact Toughness of
2.25Cr-1Mo Steel after Post Weld Heat Treatment
Hyesung Na 1 ID
, Sanghoon Lee 2 and Chungyun Kang 1, *
1 Department of Materials Science and Engineering, Pusan National University, San 30 Jangjeon-dong,
Geumjeong-gu, Busan 609-735, Korea; joyclubman@hanmail.net
2 Industrial Technology Support Division, Korea Institute of Materials Science, 797 Changwondaero,
Changwon 641-831, Korea; sanghlee@kims.re.kr
* Correspondence: kangcy@pusan.ac.kr; Tel.: +82-51-510-2852




Received: 11 May 2018; Accepted: 21 May 2018; Published: 23 May 2018


Abstract: 2.25Cr-1Mo steel with high strength at high temperatures and superior hydrogen
resistance is widely used as power generation boiler material in high-temperature and high-pressure
environments. Following the test evaluation of the ASME Boiler and Pressure Vessel Code,
specimens from the base metal of a boiler pipe were found to have impact toughness values of
386 and 28J, which are drastically different values. The analysis of the fracture surface of the 28J
test specimen revealed MnS inclusions and it was found that cracks were initiated at the inclusions.
Observation of the cross-section of the crack propagation front revealed that cracks propagated along
the ferrite regions and precipitate voids. Inclusions were also found in the 386J impact specimen.
However, the volume fraction of the inclusions was significantly less than that of the 28J specimen.
It was also found that the ferrite and carbide content of the 386J specimen was less than the 28J
specimen. The reason that the inclusions, ferrite, and carbide content differed in the two adjacent
impact test specimens was analyzed. The effects of micro-segregation such as MnS inclusions on
ferrite and carbide were compared and analyzed.

Keywords: ferrite; carbide; bainite; continuous cooling transformation (CCT) curve; charpy
impact test

1. Introduction
The 2.25Cr-1Mo Steel is widely used as a power plant boiler pipe material [1–4] due to its high
temperature creep strength, good hydrogen resistance, high toughness at high temperatures, and the
ability to withstand high pressure hydrogen atmospheres (12–21 MPa) and high temperatures (400 ◦ C
to 450 ◦ C) and pressure use environments. Due to its excellent mechanical properties, 2.25Cr-1Mo steel
is widely used not only in thermal power plants but also in nuclear power plants where high stability is
required [5]. However, 2.25Cr-1Mo steel is prone to reheating cracks after weld heat treatment (PWHT)
is performed to remove residual stress after cracking due to the thermal stress from the heating and
cooling cycles when the power plant is operating [6–8]. The integrity of the material is crucial since such
cracks can cause plant shutdowns and secondary hazards. Inspection of the components of a power
plant is carried out according to the US ASME Boiler and Pressure Vessel Code and Nuclear Power
Plant Components Certification [9]. An important quality test used to evaluate the material integrity is
the Charpy V-notch impact test of fracture toughness [10]. For the base metal of boiler tubes, the impact
test should also be tested under PWHT heat treatment conditions performed after the welding process.
However, in the special case, the impact toughness values measured from the three impact tests can
have a large variability even under the same conditions. This phenomenon occasionally occurs in
impact specimens taken from the same pipe and even at similar locations. The impact toughness of the

Metals 2018, 8, 373; doi:10.3390/met8060373 www.mdpi.com/journal/metals

Metals 2018, 8, 373 2 of 12

material is affected by many parameters such as microstructure, phases fractions and distributions,
test temperature, grain size, impact velocity, specimen shape, and notch position (sampling position of
Metals 2018, [11–18].
test specimen) 8, x FOR PEER REVIEW
In the impact test of the base metal, not many variables affect the tests2 and of 12they

are completely linked to metallurgical aspects. If the material fails to meet the impact test requirements
even at similar locations. The impact toughness of the material is affected by many parameters such
duringasa microstructure,
quality assurance inspection, it is necessary to analyze the cause and take measures to prevent
phases fractions and distributions, test temperature, grain size, impact velocity,
recurrence.
specimenIn addition,
shape, andit notch
is possible to (sampling
position prevent the recurrence
position of testby analyzing
specimen) the cause
[11–18]. In theofimpact
the variation
test
of the of
impact test and it can be utilized as a basic data of the quality defect. In this study,
the base metal, not many variables affect the tests and they are completely linked to metallurgical we analyzed
the variability
aspects. Ifofthe thematerial
impact fails
test results
to meetofthe2.25Cr-1.0Mo steel in a power
impact test requirements plant
during boiler pipe
a quality to better
assurance
inspection,
understand it is necessary
the cause to analyze the
of the variability. cause and
Through takestudies,
these measures wetohave
prevent recurrence.
found In addition,
that microsegregation
(MnS it is possibleaffects
inclusion) to prevent
phasethetransformation
recurrence by analyzing
in mztrix thestructure
cause of the
andvariation of the
this result impact test and
is considered to be a
it can be utilized as a
reference material for PWHT steel. basic data of the quality defect. In this study, we analyzed the variability of the
impact test results of 2.25Cr-1.0Mo steel in a power plant boiler pipe to better understand the cause
of the variability.
2. Experimental Through these studies, we have found that microsegregation (MnS inclusion)
Procedure
affects phase transformation in mztrix structure and this result is considered to be a reference material
The steel specimens
for PWHT steel. used in this study were SA335 GR.P22. Specimens were analyzed at the 0◦ ,
90◦ , and 180◦ positions. Composition analysis was done by optical emission spectrometer (LAB LAVM
2. Experimental
10, SPECTRO Procedure
Analytical Instruments GmbH, Kleve, Germany) and alloy components are shown in
Table 1. The steel specimens used in this study were SA335 GR.P22. Specimens were analyzed at the 0°,
90°, and 180° positions. Composition analysis was done by optical emission spectrometer (LAB
LAVM 10, SPECTRO Table 1. Chemical
Analytical composition
Instruments GmbH,of 2.25Cr-1Mo steel (wt
Kleve, Germany) %).alloy components are
and
shown in Table 1.
Chemical Composition (at. %)
Material
C Si Mn 1. Chemical
Table Cu Nicomposition
Cr Mo
of V
2.25Cr-1Mo Nb(wt %).
steel Al P S Fe
0.102 0.218 0.433 0.120 0.1246Chemical
2.0948 Composition
0.930 0.011(at. %) 0.0023 0.0251 0.0140 0.0048 Bal
Material0.097
P22 C 0.227 Si 0.443
Mn 0.124
Cu 0.1239
Ni 2.0305
Cr 0.931
Mo 0.012
V 0.0009
Nb 0.0247
Al 0.0116
P 0.0039
S Bal
Fe
0.100
0.102 0.229
0.218 0.434
0.433 0.116
0.120 0.1230 2.0051
0.1246 2.0948 0.931
0.930 0.0141 0.0023
0.011 0 0.0246
0.0251 0.0098
0.0140 0.0047 Bal
0.0048 Bal
P22 0.100
Average 0.097 0.225
0.227 0.436
0.443 0.120
0.124 0.1239 2.0305 0.931
0.1238 2.0435 0.931 0.012
0.0124 0.0009
0.0011 0.0247
0.0248 0.0116
0.0118 0.0039
0.0047 Bal
Bal
0.100 0.229 0.434 0.116 0.1230 2.0051 0.931 0.0141 0 0.0246 0.0098 0.0047 Bal
Average 0.100 0.225 0.436 0.120 0.1238 2.0435 0.931 0.0124 0.0011 0.0248 0.0118 0.0047 Bal

The base metal was PWHT annealed at 710 ◦ C for 11 h and detailed heat treatment conditions are
The base metal was PWHT annealed at 710 °C for 11 h and detailed heat treatment conditions
shown in Table 2. During the impact test of the PWHT specimens, the test specimens were randomly
are shown in Table 2. During the impact test of the PWHT specimens, the test specimens were
sampled at 1/4” thickness of the pipe (3 each × 6 set). The Charpy impact test method was tested by
randomly sampled at 1/4” thickness of the pipe (3 each × 6 set). The Charpy impact test method was
the standard
tested bytest
themethod
standardof ASTM
test methodE 23 and the
of ASTM specimen
E 23 axis was axis
and the specimen produced in the vertical
was produced direction
in the vertical
of the direction
pipe. Theofsizes of the
the pipe. Thepipe and
sizes impact
of the pipe specimens
and impact are shownare
specimens in Figure 1. Figure
shown in The impact
1. Thetest (Zwick
impact
Roell-PSW750, Ulm, Germany) was carried out at a temperature of 1 ◦ C.
test (Zwick Roell-PSW750, Ulm, Germany) was carried out at a temperature of 1 °C.

FigureFigure 1. Schematic
1. Schematic of pipe
of pipe sizesize
andand charpyV-notch
charpy V-notchimpact
impact specimen
specimen(a)
(a)pipe
pipesize (b)(b)
size single-notch.
single-notch.

Two test specimens (referred to as 386 and 28J) with appreciable differences in impact values
Two
weretest specimens
selected after (referred to as 386
impact testing andand
the28J) withofappreciable
cause differences
the difference in impact
of the impact values
values waswere
selected after impact testing and the cause of the difference of the impact values was investigated.
investigated. The fracture surfaces of the specimens was observed with a stereo microscope (optical
microscope,
The fracture OM,ofOlympus
surfaces BX-51M,
the specimens Tokyo,
was Japan)with
observed and a scanning electron microscope
stereo microscope with energyOM,
(optical microscope,
dispersive
Olympus BX-51M,X-ray spectroscopy
Tokyo, Japan)(SEM-EDX, SUPRA40VP,
and a scanning electronCarl Zeiss, Oberkochen,
microscope Germany)
with energy and their
dispersive X-ray
microstructures
spectroscopy were analyzed
(SEM-EDX, SUPRA40VP,with OM,
CarlSEM-EDX, and electronGermany)
Zeiss, Oberkochen, probe microanalysis
and their (EPMA, JXA-
microstructures
8530F, JEOL, Tokyo, Japan). Test specimens were etched with Nital (3% nitric in alcohol) and Ferrite
were analyzed with OM, SEM-EDX, and electron probe microanalysis (EPMA, JXA-8530F, JEOL, Tokyo,
Metals 2018, 8, 373 3 of 12

Japan). Test specimens were etched with Nital (3% nitric in alcohol) and Ferrite and carbide counting
was performed using ASTM E-562 (standard test for determining volume fraction) and image analysis
software (Image Pro Plus5.0, Media Cybernetics, Washington, DC, USA). The programs Thermo-Calc
TCW5 (database: TCFE6, Stockholm, Sweden, where Mats Hillert was a professor) and JMatPro
Metals 2018, 8, x FOR PEER REVIEW 3 of 12
5.1
software (Sente Software, Surrey Research Park, Guildford, UK) were used for state diagram and
and carbide
continuous cooling counting was performed
transformation (CCT)using
curveASTM E-562 (standard test for determining volume
analysis.
fraction) and image analysis software (Image Pro Plus5.0, Media Cybernetics, Washington, DC, USA).
The programs Thermo-Calc
Table 2. PWHTTCW5
(Post(database:
Weld Heat TCFE6, Stockholm,
Treatment) Sweden,
conditions where
of Cr-Mo Mats Hillert was a
steel.
professor) and JMatPro 5.1 software (Sente Software, Surrey Research Park, Guildford, UK) were
used for state diagram and continuous cooling transformation (CCT)
Condition curve analysis.
Actual
Loading Temperature 20 ◦ C
Table 2. PWHT (Post Weld Heat Treatment) conditions of Cr-Mo steel.
Heating Rate 20 ◦ C/h
Condition Actual
Holding Temperature 700–710 ◦ C
Loading Temperature 20 °C
Holding
HeatingTime
Rate 11 h
20 °C/h
Holding
Cooling Rate (above 425 ◦ C)
Temperature 700–710 ◦ C/h
20–30°C
Holding Time 11 h
Cooling Rate (above 425 °C) 20–30 °C/h
3. Results and Discussion
3. Results and Discussion
3.1. Cause Analysis of Crack Initiation Point
3.1. Cause
The Analysis
purpose of Crack
of this studyInitiation Point the variability in the impact values during impact testing.
was to analyze
As mentioned in the Experimental Procedure
The purpose of this study was to analyze section, the test specimens
the variability in the impact were randomly
values duringpicked
impact from
six sets of three
testing. sets of oneinset
As mentioned theand subjectedProcedure
Experimental to the impact test.
section, theIntest
thespecimens
total six set
weretest piece, a test
randomly
piecepicked
in thefrom
first six
setsets
with of athree
markedly different
sets of one set andimpact value
subjected was
to the found.
impact Figure
test. In the 2total
shows thetest
six set impact
valuespiece, a test
of the piece
first in thethe
set and first set with a markedly
macro-fracture different
surface impact value
photographs wastest
of each found. Figure 2The
specimen. showsimpact
the impact values of the first set and the macro-fracture surface photographs
test values of were 386, 379, and 28J, respectively. Two specimens had high impact values (386 and of each test specimen.
379J),The
butimpact test valueshad
one specimen of were 386,impact
a low 379, andvalue
28J, respectively.
of 28J. OnlyTwo onespecimens
of the sixhadtotal
highsets
impact values
(18ea) had an
(386 and 379J), but one specimen had a low impact value of 28J. Only one of the six total sets (18ea)
impact test value less than 135J (5.55%). The specimens with low impact test values is featured by a
had an impact test value less than 135J (5.55%). The specimens with low impact test values is featured
brittle fracture surface. The test specimens with high impact values were not completely destroyed nor
by a brittle fracture surface. The test specimens with high impact values were not completely
did brittle fractures
destroyed nor didappear.
brittle fractures appear.

Figure 2. Absorbed energy of Charpy impact test of steel specimens (left): a = 385J, b = 379J, c = 28J
Figure 2. Absorbed energy of Charpy impact test of steel specimens (left): a = 385J, b = 379J, c = 28J
and corresponding images of the fractured specimens (right).
and corresponding images of the fractured specimens (right).
To investigate the cause of the low impact test values, the fracture surface of the 28 and 386J test
To investigate
specimens were the causeby
examined ofSEM.
the low impact
The SEM test are
images values,
shown the fracture
in Figure surface
3. At of X1
position thein28 and 386J
Figure
3a, the 28J test
test specimens werespecimen
examined showed mostlyThe
by SEM. brittle
SEM fracture.
images It has
are flat
showncleavage fractures
in Figure with
3. At a size ofX1 in
position
Figure20~30 μm 28J
3a, the and test
particles with 2showed
specimen μm diameters
mostly show thatfracture.
brittle the river It
pattern is spreading.
has flat This part is
cleavage fractures with a
judged as the crack initiation point. When the region around X1 is enlarged, it was found that the
brittle fracture originates at a particle with about a 2 μm diameter. Particles with 2 μm diameters near
Metals 2018, 8, 373 4 of 12

size of 20~30 µm and particles with 2 µm diameters show that the river pattern is spreading. This part
is judged as the crack initiation point. When the region around X1 is enlarged, it was found that the
brittle fracture originates at a particle with about a 2 µm diameter. Particles with 2 µm diameters near
Metals
the point 2018,
X2
Metals 8, x8,FOR
were
2018, x found
FOR PEER
PEER REVIEW
to be MnS (Mn: 51.33% and S: 36.06%) when analyzed by SEM-EDX.
REVIEW 4 of4 12
of 12It has

been reported in many studies that MnS inclusions have a negative effect on mechanical properties
thethepoint
pointX2X2 werewerefoundfoundtotobe beMnS
MnS (Mn:
(Mn: 51.33% and and S:
S:36.06%)
36.06%)when whenanalyzed
analyzed byby SEM-EDX.
SEM-EDX. It has
It has
(impact, strength, elongation) [19–21]. The low impact value of the 28J specimen is caused by the MnS
beenbeenreported
reported ininmany
manystudies
studiesthat
that MnS
MnS inclusions haveaanegative
inclusions have negativeeffect
effectonon mechanical
mechanical properties
properties
inclusion.
(impact, Figure
(impact, 3b shows
strength,
strength, SEM [19–21].
elongation)
elongation) images
[19–21].Theof the
The low386J testvalue
impact
impact specimen,
value ofofthe
the28Jwhich
28Jspecimenhasisais
specimen typical
caused
causedbyductile
thethe
by MnS fracture
MnS
zone inclusion.
where MnS
inclusion. inclusions
Figure
Figure 3b3bshows were
shows SEM
SEM not observed.
images
images Regions
of the 386J
of 386J test where the
testspecimen,
specimen, inclusions
which
which has
has were
a typical
a typical expected
ductile
ductilefractureto be can
fracture
be seen
zone in where
zone various
where MnS parts
MnS of the image.
inclusions
inclusions werenot
were Itobserved.
not can be seen
observed. thatwhere
Regions
Regions it is not
where thean
the equiaxed
inclusions
inclusions weredimple
wereexpected but
expected an
to be elongated
to can
be can
dimplebe be seen
shape.
seen in in
Itvarious
can be
various parts
seen
parts ofofthe
theimage.
that image. ItIt can
can be
the elongated be seen that
thatititis
dimple
seen isisstretched
not
notan anequiaxed
in the
equiaxed dimple
notchbut
dimple ananelongated
direction.
but The shear
elongated
dimple
dimple shape.
shape. It Itcan
canbebeseen
seenthat
thatthe
the elongated
elongated dimple
dimpleisisstretched
stretchedininthe thenotch
notchdirection.
direction.The shear
The shear
ledges could also be observed.
ledges
ledges could
could alsobebeobserved.
also observed.

Figure 3. SEM observation of the fracture surface. (a) 28J; (b) 386J specimen.
Figure 3. SEM observation of the fracture surface. (a) 28J; (b) 386J specimen.
Figure 3. SEM observation of the fracture surface. (a) 28J; (b) 386J specimen.
Cross-sections of the impact test specimens were examined to investigate the presence or
absence of inclusions.
Cross-sections of the Cross-sections of the impact test specimensto were etched with theNital (3% nitric
Cross-sections of impact
the impacttest specimens were
test specimens examined
were examinedinvestigate
to investigate presence
the presence or absence
or
in alcohol).
of inclusions. Then inclusions
Cross-sections of in the
the 28J and
impact 386J
test specimens were
specimens were observed
etched with Nital
with SEM, which
(3% is shown
nitric in alcohol).
absence of inclusions. Cross-sections of the impact test specimens were etched with Nital (3% nitric
in Figure 4a,b, respectively. Observation positions were chosen to be as close to the fracture surface
Then in
inclusions in theinclusions
alcohol). Then 28J and 386Jin thespecimens
28J and 386J were observed
specimens with
were SEM, which
observed is shown
with SEM, whichin is Figure
shown 4a,b,
(red vertical lines) as possible. Inclusion shapes were examined in the region around the points X1,
respectively.
in X2,
Figure Observation
4a,b, positions
respectively. were
Observation chosen
positions to be
were as close
chosen to to
be the
as fracture
close
Y1, and Y2 in Figure 4. The inclusion sizes varied from 1 μm to 10 μm and the SEM-EDX to thesurface
fracture (red vertical
surface
lines)(red vertical lines)
ascomposition
possible. as
Inclusionpossible. Inclusion shapes were examined in the region around the
analysis revealed that the inclusions consisted of a complex oxide of Al oxide, MnS, and and Y2
shapes were examined in the region around the points X1, points
X2, Y1, X1,
X2,
in Figure Y1,
Al 4. and
TheThe
oxide. Y2 in Figure
inclusion
inclusionsizes4. and
size Thevolume
variedinclusion
from 1sizes varied
µmofto
fraction 10386J
the µm from
and1 the
impact μm to 10were
SEM-EDX
specimen μm less
and the those
composition
than SEM-EDXofanalysis
composition
revealedthe 28Jthe
that analysis
impact revealed
specimen.
inclusions consisted of a complex oxide of Al oxide, MnS, and Al oxide. MnS,
that the inclusions consisted of a complex oxide of Al oxide, and
The inclusion
Al oxide. The inclusion size and volume fraction of the 386J impact specimen were less than those of
size and volume fraction of the 386J impact specimen were less than those of the 28J impact specimen.
the 28J impact specimen.

Figure 4. OM and SEM images of inclusions in the cross-section of the (a) 28J and (b) 386J specimen.

Figure
Figure 4. OM4. OM
andand
SEMSEM images
images ofof inclusionsin
inclusions in the
the cross-section
cross-section ofofthe (a)(a)
the 28J28J
andand
(b) (b)
386J386J
specimen.
specimen.
Metals 2018, 8, 373 5 of 12
Metals 2018, 8, x FOR PEER REVIEW 5 of 12
Metals 2018, 8, x FOR PEER REVIEW 5 of 12
It has
It has been
been reported
reported in in the
the literature
literature that that the
the inclusion
inclusion volume
volume fraction
fraction affects
affects thethe impact
impactvalue,
value,
which It has
means
which means been thereported
inclusion in the
(MnS, literature
AlO) that
volume the inclusion
fraction hasvolume
been fraction
measured.
inclusion (MnS, AlO) volume fraction has been measured. To accurately measure affects
To the impact
accurately value,
measure
which
the means volume
the inclusion
inclusion the
volumeinclusion
fraction
fraction (MnS, of AlO)
of the
the two
two volume fraction has
test specimens,
test specimens, EPMA
EPMA beenback-scatter
measured. To
back-scatter accurately
electron
electron measure
detector
detector (BSE)
(BSE)
the inclusion
images
images were volume
were collected
collected fraction
and
andareare of the two
shown
shown test
in Figure
in specimens,
5. In5.the
Figure EPMA
Inimages
the back-scatter
from
images the
from theelectron
EPMA-BSE,EPMA-BSE, detector
elements (BSE)
heavier
elements
images
or lighter
heavier were
orthan collected
lighter Fe can
thanbeand are be
Feobserved.
can shown Theinelements
observed. Figure
The 5. Al,InMn,
elementsthe S,images
Al, andMn,Ofrom
in
S, the
andtheOEPMA-BSE,
MnS inandthe AlO elements
MnSinclusions
and AlO
heavier or
are lighterare
inclusions lighter
than than
Fe and
lighter Fe
thanappearcan be observed.
Fe andasappearblack as The
regions elements Al,
in the EPMA-BSE
black regions Mn,
in the EPMA-BSES, and O in
images.images. the MnS
For 2.25Cr-1Mo and steel,
For 2.25Cr-1Mo AlO
inclusions
M23C6
steel, and
M23C6 are M6Clighter
and than
precipitates
M6C Fe and
precipitates appear
are observed as[22,23].
are observed black[22,23].
regions
One ofOnein the
the EPMA-BSE
main
of the elements images.
of the of
main elements For
the2.25Cr-1Mo
precipitate is Mo,
precipitate
steel,
which
is M23C6
Mo, which and
is heavier M6C
than FE
is heavier precipitates
than andFEappears are
and appearsobserved
as white [22,23].
regions
as white One of the main
in theinEPMA-BSE
regions elements
the EPMA-BSE images of the precipitate
[24]. [24].
images Figure 5a,b
Figure
is Mo,shows
shows
5a,b which
the 28theis
and heavier
28386J than
386JFE
andspecimens, and appears
respectively.
specimens, as Black
white inclusions
respectively. regions in and
the EPMA-BSE
Black inclusions white images
precipitates
and white [24].
are Figure
observed
precipitates are
5a,b
in shows
both the
specimens. 28 and 386J
However, specimens,
the 386J respectively.
specimen shows Black
fewer
observed in both specimens. However, the 386J specimen shows fewer black inclusions than the 28Jinclusions
black and
inclusions white
than precipitates
the 28J are
specimen.
observed
To determine
specimen. inToboth thespecimens.
determineinclusion However,
(MnS, AlO)
the inclusion thevolume
(MnS, 386J
AlO)specimen
volume shows
fraction, fewer
we measured
fraction, black
theinclusions
we measured total thesize than
totalofsizethe
the 28J
black
of the
specimen.
inclusion
black To determine
regions
inclusion in 12 BSE
regions the
in inclusion
images
12 BSE using (MnS,
images AlO)
image volume
image fraction,
usinganalysis analysis we
software measured
(image
software Pro the total
Plus).
(image size
ThePlus).
Pro of The
measuredthe
black
resultsinclusion
measured areresults
shown regions
in Figure
are shown in 126.in BSE
Figure images
6. using image analysis software (image Pro Plus). The
measured results are shown in Figure 6.

Figure
Figure 5.
5. Counting
Counting inclusion
inclusion using
using EPMA-BSE
EPMA-BSE image
image (a)
(a) 28J
28J and
and (b)
(b) 386J
386J Specimen.
Specimen.
Figure 5. Counting inclusion using EPMA-BSE image (a) 28J and (b) 386J Specimen.
The inclusion volume fraction was about 0.8% for the 28J specimen and 0.1% for the 386J
The inclusion volume fraction was about 0.8%0.8%
for the 28J specimen and 0.1% for0.1%
the 386J
for specimen.
specimen.inclusion
The Therefore, volume fraction
the inclusion was
volume about
fraction in for
the the 28J specimen
28J specimen and
is about eight times the 386J
greater
Therefore,
specimen. the inclusion
Therefore, the volume
inclusion fraction
volume in the
fraction28J inspecimen
the 28J is about
specimen eight
is times
about greater
eight times than the
greater
than the 386J specimen. One of the reasons for the low impact value of the 28J specimen is that the
386J
than specimen.
thevalue One
386J specimen. of the
One reasons for the low impact value of the 28J specimen is that the impact
impact decreases as theofinclusion
the reasons for the
volume low impact
fraction value
increases. of isthe
This 28J specimen
consistent with aisprevious
that the
value decreases
impact value as the inclusion
decreases as the volume
inclusion fraction
volume increases.
fraction This isThis
increases. consistent
is with awith
consistent previous
a result
previous
result reported in the literature [25]. It is evident that the inclusion volume fraction varies greatly
reported
result in the
reported literature
in the [25].
literature It is evident that the inclusion volume fraction varies greatly between
between specimens even within [25]. It is pipe.
the same evident
This that
hasthe
beeninclusion
attributedvolume fraction
to a casting varies
defect greatly
caused by
specimens
between even within the same pipe. This has been attributed to a casting defect caused by the local
the local specimens
incorporation evenofwithin the same
inclusions during pipe. This has
melting andbeen attributed
casting [26]. to a casting defect caused by
incorporation
the of inclusions
local incorporation during melting
of inclusions during and casting
melting and[26].
casting [26].

Figure 6. The experimentally measured specimens and the amount of inclusions.

Figure
Figure6.6.The
Theexperimentally
experimentallymeasured
measuredspecimens
specimensand
andthe
theamount
amountof
ofinclusions.
inclusions.
3.2. Cause Analysis of Crack Propagation
3.2. Cause Analysis of Crack Propagation
As stated above, crack initiation starts at an inclusion. Cross-sections of the impact specimens
As stated above,
were observed by SEM crack initiation
to identify thestarts at the
path of an inclusion. Cross-sections
cracks generated of the impact
by the inclusions. The specimens
OM image
were
shown in Figure 7a shows the macrostructure of the cross-section of the 28J impact testOM
observed by SEM to identify the path of the cracks generated by the inclusions. The image
specimen.
shown in shows
Figure 7b Figure an
7a SEM
shows the macrostructure
image of the cross-section
of the region highlighted of the in
by the red square 28JFigure
impact
7a.test
Thespecimen.
specimen
Figure 7b shows an SEM image of the region highlighted by the red square in Figure 7a. The specimen
Metals 2018, 8, 373 6 of 12

3.2. Cause Analysis of Crack Propagation

As stated above, crack initiation starts at an inclusion. Cross-sections of the impact specimens
were observed by SEM to identify the path of the cracks generated by the inclusions. The OM image
shown in Figure 7a shows the macrostructure of the cross-section of the 28J impact test specimen.
Figure 7b shows an SEM image of the region highlighted by the red square in Figure 7a. The specimen
was tilted to show the fracture surface well and then was observed by SEM. By observing from the
side of Metals
the fracture surface,
2018, 8, x FOR it is seen that the movement path of the crack can be one of
PEER REVIEW 6 oftwo
12 types.
One type of crack propagation occurs across the ferrite, which is seen in Figure 7 (cracks across bainite
was tilted to show the fracture surface well and then was observed by SEM. By observing from the
were not observed while crack propagation across ferrite was easily observed).
side of the fracture surface, it is seen that the movement path of the crack can be one of two types.
In One
the second typepropagation
type of crack of crack propagation, a micro-void
occurs across the ferrite, whichisisgenerated
seen in Figurearound theacross
7 (cracks carbide located at
bainite
the grain boundary and cracks migrate along the micro-void. Impact
were not observed while crack propagation across ferrite was easily observed). values are known to correlate
with grain In size
the[17].
secondAtype smaller
of crackgrain size yields
propagation, better is
a micro-void impact values
generated around andthebainite with fine
carbide located at grain
the grainwell
size performs boundary and cracks
in impact migrate
tests. Thisalong
is thethereason
micro-void.
that Impact values
the crack are known to
propagates correlate
along the ferrite.
with grain size
When precipitates [17].
are A smaller
present, grain
it is size yields
known that better impactM23C6
the coarse values and bainiteand
carbide withM7C3
fine grain
aresize
formed at
performs well in impact tests. This is the reason that the crack propagates along the ferrite. When
the grain boundary [22,23]. M23 C6 carbides and M7 C3 carbide are incoherent boundaries with the
precipitates are present, it is known that the coarse M23C6 carbide and M7C3 are formed at the grain
matrix structure. Due toMthe
boundary [22,23]. incoherent boundaries, there is a small gap between the matrix and the
23C6 carbides and M7C3 carbide are incoherent boundaries with the matrix

precipitate. (The size of the

structure. Due to the incoherentgap is anboundaries,
atomic size.)thereWhen a small
is a small gapforce
betweenis applied
the matrixto these
and the gaps, the
precipitate.
gap grows into micro (The voids
size ofby
thestress
gap is concentration.
an atomic size.) When a smallour
Therefore, force is applied
results showtothat
thesecracks
gaps, the
propagate
gapmicro-voids
along the grows into micro voidsthe
around by stress concentration.
precipitate of the Therefore, our resultsor
grain boundaries show that cracks
across propagate
the ferrite.
along the micro-voids around the precipitate of the grain boundaries or across the ferrite.
From the results shown in Figure 7, the effect of the ferrite and carbide on the impact properties
From the results shown in Figure 7, the effect of the ferrite and carbide on the impact properties
was estimated by comparing and analyzing the textures of the 28J and 386J impact test specimens.
was estimated by comparing and analyzing the textures of the 28J and 386J impact test specimens.

Figure 7. Microstructure of the 28J specimen cross-section. (a) OM image; (b) SEM image; (c,d) SEM
Figure 7. Microstructure
image of theby28J
of regions enlarged thespecimen
red squarescross-section.
in (b). (a) OM image; (b) SEM image; (c,d) SEM
image of regions enlarged by the red squares in (b).
3.2.1. Effect of Ferrite on Impact Value
3.2.1. EffectFigure
of Ferrite
8 is aon Impact Value
microstructure photograph of the (a) 28J impact test specimen and (b) 386J test
specimen. Figure 8c shows the elongated ferrite + bainite structure of the 28J specimen and (d) shows
Figure 8 is a microstructure photograph of the (a) 28J impact test specimen and (b) 386J test
the unstretched ferrite + bainite structure of the 386J specimen. The bainite + ferrite structure in Figure
specimen.8C isFigure 8c shows
elongated in the the elongated
direction of the ferrite + bainite
impact test structure
while Figure of thethat
8d shows 28J the
specimen
bainite +and (d) shows
ferrite
the unstretched
structure isferrite + bainite
not elongated. Thestructure of the
ferrite fraction 386J
of (c) wasspecimen.
higher than The
that ofbainite
(d). The+fraction
ferriteofstructure
the in
ferrite was measured by the ASTM-E562 method by taking 16 OM images from the regions
Figure 8c is elongated in the direction of the impact test while Figure 8d shows that the bainite + ferrite left of the
structureredislines
notinelongated.
Figure 8a,b.The ferrite fraction of (c) was higher than that of (d). The fraction of the
Figure 9 shows the fraction of ferrite, which is measured from OM images. For the 386J test
ferrite was measured by the ASTM-E562 method by taking 16 OM images from the regions left of the
specimens, the average ferrite fraction was 65.15% while the 28J specimen showed a high average
red lines in Figure
ferrite 8a,b.
fraction of 83.51%. Therefore, we conclude that a higher ferrite fraction yields a lower impact
Figure 9 shows
value. The reason theforfraction ofasferrite,
this is that, which
the fraction is measured
of ferrite increases,from OM images.
the fraction of bainite For the 386J test
decreases.
specimens, the average
The impact ferrite fraction
value is lowered due to thewas 65.15%
decrease in thewhile the
fraction of 28J specimen
the bainite, whichshowed a high average
has a satisfactory
impact value.
ferrite fraction The ferrite
of 83.51%. fraction ofwe
Therefore, theconclude
test specimens
thathaving an impact
a higher ferritevalue of 135J
fraction was measured
yields a lower impact
for 18 specimens by the same method. In Figure 9b, the reliability is low due to the small number of
test specimens. However, it can be seen that the correlation between ferrite fraction and the impact
value is linear. It is also possible to present a guideline for the fraction of ferrite required to yield the
Metals 2018, 8, 373 7 of 12

value. The reason for this is that, as the fraction of ferrite increases, the fraction of bainite decreases.
The impact value is lowered due to the decrease in the fraction of the bainite, which has a satisfactory
impact value. The ferrite fraction of the test specimens having an impact value of 135J was measured
for 18 specimens by the same method. In Figure 9b, the reliability is low due to the small number of
test specimens. However, it can be seen that the correlation between ferrite fraction and the
Metals 2018, 8, x FOR PEER REVIEW
impact
7 of 12
value isMetals
linear.
2018,It8,is alsoPEER
x FOR possible
REVIEW to present a guideline for the fraction of ferrite required7 to yield the
of 12

minimum
minimum required
required impact
impactvalue,
value,but
butthis
thiswould
would require theanalysis
require the analysisof of more
more specimens.
specimens. The two
The two
minimum required impact value, but this would require the analysis of more specimens. The two
specimens
specimens shown in Figure 9a are from the same pipe. The reason for the large difference
shown in Figure 9a are from the same pipe. The reason for the large difference in their in their
specimens shown in Figure 9a are from the same pipe. The reason for the large difference in their
volumevolume fractions
fractions is discussed
is discussed below.
below.
volume fractions is discussed below.

Figure 8. Microstructure of the base metal: (a) 386J specimen and (c) is (a) part enclosed with a red
Figure 8. Microstructure
Figure of of
8. Microstructure thethe
base
basemetal:
metal: (a)
(a) 386J specimenand
386J specimen and
(c)(c)
is is
(a)(a) part
part enclosed
enclosed withwith
a reda red
square; (b) 21 specimen and (d) is (a) part enclosed with a red square.
square; (b) 21
square; (b)specimen
21 specimenandand
(d)(d)
is is
(a)(a)part
partenclosed
enclosed with
with aa red
redsquare.
square.

Figure 9. Relationship between volume fraction of ferrite and impact value (a) Volume fraction of
ferrite for 386J and 28J specimens and (b) liner analysis of impact value and fraction of ferrite.
Figure 9. Relationship between volume fraction of ferrite and impact value (a) Volume fraction of
Figure 9. Relationship between volume fraction of ferrite and impact value (a) Volume fraction of
ferrite for 386J and 28J specimens and (b) liner analysis of impact value and fraction of ferrite.
The
ferrite for 28Jand
386J and28J
386J test specimens
specimens and (b)contained different
liner analysis volume
of impact fractions
value of inclusions,
and fraction which
of ferrite.
contained MnS. The amount of Mn in MnS is about 60%. Therefore, it is reported that a depleted zone
The 28J and 386J test specimens contained different volume fractions of inclusions, which
of Mn is formed around MnS and this depleted part promotes ferrite formation [27,28]. Therefore,
The 28J
contained and 386JThe
MnS. testamount
specimens
of Mncontained different
in MnS is about 60%.volume fractions
Therefore, of inclusions,
it is reported which contained
that a depleted
the volume fraction of ferrite was higher in the 28J impact test specimen because it contained more
zone
of
MnS. The Mn
MnS is formed
amount around
of Mn
inclusions than in MnS
theMnS and this depleted
is about 60%.
386J specimen. part
Therefore,
The matrix promotes ferrite
it is reported
composition formation [27,28].
that a depleted
has been described Therefore,
zone
previously as aof Mn is
formedthechange
volume
around fraction
inMnS
the Mnand ofthis
ferrite
content was
depleted
of the higher
matrix duein
part tothe
the28J
promotes impact
volumeferritetest specimen
formation
fraction becauseTherefore,
[27,28].
in MnS inclusions. it contained
The themore
composition volume
MnS
fractionof inclusions
ofMn in the
ferrite than
matrix
was the
when
higher 386J
inthespecimen.
thevolume The matrix
fraction
28J impact composition
testofspecimen
inclusions because has
are 0% and been described
about 0.3% more
it contained previously
was calculated.as a
MnS inclusions
changecalculated
in the Mn alloy
content of the matrix due tointhe volume fraction
a CCT in MnScreated
inclusions. The composition
than theThe
386J specimen. composition
The is shown
matrix composition Figure 10 by
has been described curve previously using
as Jmat-Pro.
a changeThein the Mn
of Mn content
in the matrix when the volume fraction of inclusions are 0% and
of the matrix at 0% and 0.3% inclusions decreases from 0.436 to 0.256%. about 0.3% was calculated.
content of the matrix due to the volume fraction in MnS inclusions. The composition of Mn in the
The calculated alloy composition is shown in Figure 10 by a CCT curve created using Jmat-Pro. The
matrix when [Totalfraction
theofvolume measuredofMn content (0.436%) =and
0.05% X Mn0.3%
content in MnS (60%) + The calculated
Mn content the matrix at 0% andinclusions are 0%
0.3% inclusions decreasesabout
from 0.436was calculated.
to 0.256%.
Mn content of matrix at 0.3% inclusions]
alloy composition is shown in Figure 10 by a CCT curve created using Jmat-Pro. The Mn content of the
matrix at 0%Asand [Total
0.3% measureddecreases
inclusions Mn content (0.436%)
from 0.436 = 0.05% X Mn content in MnS (60%) +
a result, the ferrite CCT curve moves to the leftto
as0.256%.
the amount of Mn decreases from 0.436 to
Mn content of matrix at 0.3% inclusions]
0.256%. At the same cooling rate (0.1 °C/s), ferrite content increases as the ferrite moves toward
[Total
shorter timesmeasured
along Mn content
the curve. as(0.436%) = 0.05% X Mnincreases,
content the
in MnS (60%) + in the
As a result, the ferrite CCTThat is, moves
curve the amount of inclusions
to the left as the amount amount
of Mn decreasesoffrom
Mn 0.436 to
0.256%. At the same cooling Mnrate
content of matrix
(0.1 °C/s), ferriteatcontent
0.3% inclusions]
increases as the ferrite moves toward
shorter times along the curve. That is, as the amount of inclusions increases, the amount of Mn in the
Metals 2018, 8, 373 8 of 12

As a result, the ferrite CCT curve moves to the left as the amount of Mn decreases from 0.436
to 0.256%. At the same cooling rate (0.1 ◦ C/s), ferrite content increases as the ferrite moves toward
shorter Metals
times2018,
along thePEER
8, x FOR curve. That is, as the amount of inclusions increases, the amount8ofof Mn
REVIEW 12 in the
matrix decreases. As the amount
Metals 2018, 8, x FOR PEER REVIEW
of Mn in the matrix decreases, the ferrite CCT curve moves to
8 of 12
the left
matrix decreases. As the amount of Mn in the matrix decreases, the ferrite CCT curve moves to the
and the content of ferrite increases even at the same cooling rate.
left and the content of ferrite increases even at the same cooling rate.
matrix decreases. As the amount of Mn in the matrix decreases, the ferrite CCT curve moves to the
left and the content of ferrite increases even at the same cooling rate.

Figure 10. CCT curves for different volume fraction of alloying elements calculated by a Jmat-Pro
Figure 10. CCT curves for different volume fraction of alloying elements calculated by a Jmat-Pro simulation.
simulation.
Figure 10. CCT curves for different volume fraction of alloying elements calculated by a Jmat-Pro
simulation.
3.2.2. Effect
3.2.2. of Carbide
Effect on Impact
of Carbide Value
on Impact Value

The The
3.2.2. microstructure
Effect of Carbide
microstructure inImpact
in on regions
regions aroundthe
Value
around the carbide
carbide ininthe 28J28J
the andand
386J386J
specimens was observed.
specimens was observed.
Figure
Figure 11 shows 11 shows a cross-sectional
a cross-sectional SEMSEM image
image of both
of both specimens. Inter-granular white spherical
The microstructure in regions around the carbide in specimens.
the 28J and 386JInter-granular white spherical
specimens was observed.
precipitates are observed and precipitates are observed in the prior austenite grain boundary. The
Figureare
precipitates 11 shows a cross-sectional
observed SEM image
and precipitates are ofobserved
both specimens.
in theInter-granular whitegrain
prior austenite spherical
boundary.
precipitates of Figure 11d have greater spacing and are larger in size than the prior austenite grain
precipitates
The precipitates ofare observed
Figure 11d and precipitates
have greater are observed
spacing and in the
are prior
larger in austenite
size grain
than the boundary.
prior The grain
austenite
boundary precipitates of (c).
precipitates of Figure 11d have greater spacing and are larger in size than the prior austenite grain
boundary precipitates of (c).
boundary precipitates of (c).

Figure 11. SEM image of the base metal (a) 386J and enlarged red square (c); (b) 28J and enlarged red
square (d).
Figure 11. SEM image of the base metal (a) 386J and enlarged red square (c); (b) 28J and enlarged red
Figure 11. SEM image of the base metal (a) 386J and enlarged red square (c); (b) 28J and enlarged red
square (d).
square (d).
Metals 2018, 8, 373 9 of 12
Metals 2018, 8, x FOR PEER REVIEW 9 of 12

For reliable
For reliablemeasurements,
measurements, Murakami
Murakami etching
etching and aand a precipitate
precipitate etchingetching
solutionsolution of prior
of prior austenite
austenite grain boundary was performed. The amount and size of the precipitates were
grain boundary was performed. The amount and size of the precipitates were measured by using measured by
using Image Pro plus. The size and size distributions of the precipitates are shown in Figure 12. The
Image Pro plus. The size and size distributions of the precipitates are shown in Figure 12. The results in
results in Figure 12 show that the size and amount of 28J specimen precipitates are larger than the
Figure 12 show that the size and amount of 28J specimen precipitates are larger than the 386J specimen.
386J specimen. These results suggest that a large amount of large precipitates in the 28J specimen is
These results suggest that a large amount of large precipitates in the 28J specimen is generated by
generated by micro-voids due to the incoherent boundary with the matrix and then micro-voids are
micro-voids due to the incoherent boundary with the matrix and then micro-voids are combined
combined to propagate cracks. From the results shown in Figures 11 and 12, the difference of the
to propagate cracks. From the results shown in Figures 11 and 12, the difference of the precipitates
precipitates present in the two impact test specimens was investigated.
present in the two impact test specimens was investigated.

Figure 12. Histogram

Figure 12. Histogram of
of aa carbide
carbide in
in 386J
386J and
and 28J
28J specimens.
specimens.

Figure 13a
Figure 13a shows
shows aa well-known
well-known Fe-C
Fe-C phase
phase diagram.
diagram. In In the
the Fe-C
Fe-C phase
phase diagram,
diagram, the
the C solubility
solubility
in the
in the ferrite
ferrite is
is 0.025%.
0.025%. Figure 13b is a state state diagram
diagram of of carbon
carbon content
content inin 2.25Cr-1Mo
2.25Cr-1Mo steel steel using
using
Thermo-calc. Additionally,
Thermo-calc. Additionally,the theCCsolubility
solubility in
inthe
the ferrite
ferrite isis 0.009%.
0.009%. TheThe amount
amount of of C
C solubility
solubility varies
varies
depending on
depending on the
the alloying
alloying elements.
elements. Solubility of C was low in the state calculated by Thermo-Calc.
This is
This is probably
probably duedue to to the
the phase
phase ofofM23C6,
M23C6, which
which takes
takes carbon
carbon from
from multiple
multiple systems.
systems. In In order
order toto
make aa more
make more conservative
conservative judgment,
judgment, modeling
modeling waswas performed
performed by by calculating
calculating the
the amount
amount of of ferrite
ferrite
cabon solubility
cabon solubility as as 0.025%.
0.025%.
Modeling of
Modeling of the
the carbon
carbon chemical
chemical concentration
concentration shows
shows that that the
the C
C content
content of
of ferrite
ferrite is
is 0.025%
0.025% and and
the C content of the base metal is 0.1% (see Figure 13c). The content
the C content of the base metal is 0.1% (see Figure 13c). The content of C (0.1% − of C (0.1% − 0.025% = 0.075%)
must be
must be contained
contained in in the
the other
other constituent
constituent other
other than
than ferrite.
ferrite. The
The higher
higher the
the ferrite
ferrite content,
content, the
the higher
higher
the content of
the of CCisisininthetheother
otherconstituent
constituentincluding
includingcalculating
calculatingthe the
amount
amountof carbon in theinother
of carbon the
constituent.
other constituent.

-- 28J:
28J: 0.1%
0.1% CC Base
Base Metal Composition =
Metal Composition = 83.51%
83.51% Ferrite Volume Fraction
Ferrite Volume FractionXX0.025%
0.025%CC++ CC content
content of
of
16.49% the
16.49% the other
other constituent
constituent ==>
==> CCcontent
contentof
of16.49%
16.49%the
the other
other constituent
constituent ==0.4798%
0.4798%
- 386J: 0.1% C Base Metal Composition = 64.76% Ferrite Volume Fraction X 0.025% C + C content
- 386J: 0.1% C Base Metal Composition = 64.76% Ferrite Volume Fraction X 0.025% C + C content
of 35.24% the other constituent ==> C content of 35.24% the other constituent = 0.2378%
of 35.24% the other constituent ==> C content of 35.24% the other constituent = 0.2378%
For this reason, the amount of precipitate generated is due to the fact that the carbon content of
For this reason, the amount of precipitate generated is due to the fact that the carbon content of
the other constituent in PWHT is twice as much as that of the other constituent of 386J.
the other constituent in PWHT is twice as much as that of the other constituent of 386J.
Figure 14 shows the results of EPMA analysis of the 28J impact specimen. It can be seen that
Figure 14 shows the results of EPMA analysis of the 28J impact specimen. It can be seen that
there is a large amount of precipitate in the prior austenite grain boundaries. The precipitates consist
there is a large amount of precipitate in the prior austenite grain boundaries. The precipitates consist
of Cr, Mo, Mn, and C and, in particular, precipitates with a higher content Cr and C were found.
of Cr, Mo, Mn, and C and, in particular, precipitates with a higher content Cr and C were found.
Usually, the precipitates with a higher content of Cr and C than M23C6 precipitates are supposed to
Usually, the precipitates with a higher content of Cr and C than M23C6 precipitates are supposed to be
be M7C3. In addition to forming incoherent boundaries between the matrix and precipitate by the
M7C3. In addition to forming incoherent boundaries between the matrix and precipitate by the HCP
HCP crystal structure, they form a surrounding Cr-depleted zone due to the high interrelation of Cr
crystal structure, they form a surrounding Cr-depleted zone due to the high interrelation of Cr and C.
and C. Excess Cr-rich precipitates in the prior austenite grain boundaries cause Cr-depleted zone
formation around the precipitate, which softens the grain boundaries and becomes vulnerable to
Metals 2018, 8, 373 10 of 12

Excess Cr-rich precipitates in the prior austenite grain boundaries cause Cr-depleted zone formation
Metals 2018, 8, x FOR PEER REVIEW 10 of 12
Metals 2018,
around the8,precipitate,
x FOR PEER REVIEW
which softens 10 of 12
the grain boundaries and becomes vulnerable to stress corrosion
cracking
stress when the
corrosion Cr content
cracking whendecreases [29,30].decreases
the Cr content It should[29,30].
also be Itnoted thatalso
should these
be precipitates may
noted that these
stress the
affect corrosion cracking
physical when
properties of the HAZ
the Cr content
during decreases
welding [29,30]. It should also be noted that these
[11].
precipitates may affect the physical properties of the HAZ during welding [11].
precipitates may affect the physical properties of the HAZ during welding [11].

Figure
Figure 13.
13.Schematic
Schematicof calculation of carbon
of calculation contents
of carbon in thein
contents other
the constituent (a) Fe-C(a)
other constituent phase diagram
Fe-C phase
Figure 13. Schematic of calculation of carbon contents in the other constituent (a) Fe-C phase diagram
(b) 2.25Cr-1Mo
diagram Steel
(b) 2.25Cr-1Mo + C phase diagram calculated using Thermo-calc (c) modeling of
of carbon
(b) 2.25Cr-1Mo Steel + Steel + C phase
C phase diagram
diagram calculated
calculated using
using Thermo-calc
Thermo-calc (c)(c)modeling
modelingof carbon
carbon
concentration
concentration between ferrite
ferrite and the
the other constituent.
constituent.
concentration between
between ferrite and
and the other
other constituent.

Figure 14. EPMA images of the 28J impact specimen. (a) composite image (b) chromium (c) carbon
Figure 14.
14. EPMA
EPMA images
images of
of the
the 28J
28J impact
impact specimen. (a) composite image (b) chromium (c) carbon
Figure
(d) molybdenum (e) manganese (f) sulfur. specimen. (a) composite image (b) chromium (c) carbon
(d) molybdenum (e) manganese (f) sulfur.
(d) molybdenum (e) manganese (f) sulfur.
4. Conclusions
4. Conclusions
4. Conclusions
The MnS and other inclusions in the 28J impact specimen were found to be larger than the 386J
The MnS
The MnS andand other
other inclusions
inclusions inin the
the 28J impact
28J impact specimen
specimen were found to be larger
larger than
than thethe 386J
386J
specimen. At the same cooling rate, the ferrite content of the basewere metal found to be
is increased as the ferrite CCT
specimen. At
specimen. the
At to same
thethe
same cooling rate, the ferrite
ferrite content of the base metal is
is increased as
as the ferrite CCT
curve moves left cooling
due to therate,
Mn thedeficiency content
caused of by
thethe
base MnSmetal increased
formation. As the the ferrite
ferrite CCT
content
curve
curve moves
moves to
to the
the left
left due
due to
to the
the Mn
Mn deficiency
deficiency caused
caused by
by the
the MnS
MnS formation.
formation. As
As the
the ferrite
ferrite content
content
increases, the impact value is lowered due to the decrease of the bainite, which has high impact test
increases, the
increases, the impact
impact value
value is
is lowered
lowered due to
due to the
the decrease
decrease of of the
the bainite,
bainite, which has has high impact
impact test
test
values. The increase of ferrite content increases the C content of the otherwhich
constituenthigh due to the low
values. The
values. The increase
increase of ferrite content increases the CC content of
of the other
other constituent due to
to the
the low
C content (0.025%) ofof ferrite
ferrite content
(about increases
0.4798%). theresults
This content
in a large theamount constituent
of precipitatedue(M23C6) low
in
C
C content
content (0.025%)
(0.025%) of
offerrite
ferrite (about
(about 0.4798%).
0.4798%). This
Thisresults
resultsinina large
a largeamount
amount of precipitate
of precipitate (M23C6)
(M23C6) in
the prior austenite grain boundaries and coarse Cr precipitates are the migration path of cracks in
the prior austenite grain
in the prior generation.
austenite grain boundaries and coarse Cr precipitates are the migration path of cracks in
micro-void Theboundaries
occurrence and coarse Cr precipitates
of Cr-depleted zones leadsare the migration
to softening of the path of austenite
prior cracks in
micro-void generation.
micro-void generation. TheThe occurrence
occurrence of
of Cr-depleted
Cr-depleted zones leads
zones leads toto softening
softening ofof the
the prior
prior austenite
austenite
grain boundaries, which can be expected to weaken the stress corrosion cracking of these areas.
grain boundaries,
grain boundaries, which
which cancan be
be expected
expected to to weaken
weaken the the stress
stress corrosion
corrosion cracking
cracking of of these
these areas.
areas.
Author Contributions: S.L. and C.K. conceived and designed the experiments. H.N. performed the experiments
Author Contributions:
Contributions: S.L. and C.K. conceived and designed the experiments. H.N. performed the experiments
Author
and analyzed the data. S.L. and C.K. conceived and designed the experiments. H.N. performed the experiments
and analyzed the data.
Acknowledgments: This work was supported by a National Research Foundation of Korea (NRF) grant funded
Acknowledgments: This work was supported by a National Research Foundation of Korea (NRF) grant funded
by the Korean government (MSIP) (No. 2012R1A5A1048294).
by the Korean government (MSIP) (No. 2012R1A5A1048294).
Conflicts of Interest: The authors declare no conflict of interest. The funding sponsors had no role in the design
Conflicts of Interest: The authors declare no conflict of interest. The funding sponsors had no role in the design
of the study, in the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the
of the study, in the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the
decision to publish the results.
decision to publish the results.
Metals 2018, 8, 373 11 of 12

Acknowledgments: This work was supported by a National Research Foundation of Korea (NRF) grant funded
by the Korean government (MSIP) (No. 2012R1A5A1048294).
Conflicts of Interest: The authors declare no conflict of interest. The funding sponsors had no role in the design of
the study, in the collection, analyses, or interpretation of data, in the writing of the manuscript, or in the decision
to publish the results.

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