Materials Science & Engineering A 658 (2016) 5059

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Effect of surface grinding on chloride induced SCC of 304L

Nian Zhou a,b,n, Rachel Pettersson b,c, Ru Lin Peng d, Mikael Schnning e
a
Department of Material Science, Dalarna University, SE-79188 Falun, Sweden
b
KTH, SE-10044 Stockholm, Sweden
c
Jernkontoret, SE-11187 Stockholm, Sweden
d
Department of Management and Engineering, Linkping University, SE-58183 Linkping, Sweden
e
Corrosion Department, Avesta Research Centre Outokumpu Stainless AB, SE-774 22 Avesta, Sweden

art ic l e i nf o a b s t r a c t

Article history: The effect of surface grinding on the stress corrosion cracking (SCC) behavior of 304L austenitic stainless
Received 21 December 2015 steel in boiling magnesium chloride has been investigated. SCC tests were conducted both without ex-
Accepted 25 January 2016 ternal loading and with varied levels of four-point bend loading for as-delivered material and for spe-
Available online 29 January 2016
cimens which had been ground parallel or perpendicular to the loading direction. Residual stresses due
Keywords: to the grinding operation were measured using the X-ray diffraction technique. In addition, surface stress
Stress corrosion cracking measurements under applied load were performed before exposure to evaluate the deviation between
Residual stress actual applied loading and calculated values according to ASTM G39. Micro-cracks initiated by a high
Austenitic stainless steel 304L level of tensile residual stress in the surface layer were observed for all the ground specimens but not
Grinding
those in the as-delivered condition. Grinding along the loading direction increased the susceptibility to
chloride induced SCC; while grinding perpendicular to the loading direction improved SCC resistance.
Surface tensile residual stresses were largely relieved after the initiation of cracks.
& 2016 Elsevier B.V. All rights reserved.

1. Introduction environment than solution annealed material. A higher surface

Standard austenitic stainless steels are very widely used for
industrial applications. However, they are highly susceptible to
chloride stress corrosion cracking (SCC) which can lead to cata-
strophic failures. One review in 1983 showed that 37% of almost
one thousand failure cases of the austenitic stainless steel 304 in
the chemical industry were attributed to stress corrosion cracking
[1]. Depending on the microstructure of the material and the
nature of the environment, SCC may be intergranular or trans-
granular [2]. For example, Ghosh and Kain observed cracking to be
transgranular for solution annealed, cold worked and surface
machined 304L stainless steel in a chloride environment [3]. Jin
et al. [4] showed grain boundary engineering could shift the
fracture from intergranular to transgranular stress corrosion
cracking of 304 stainless steel plate.
It is well recognized that the surface conditions including
geometrical, physical and mechanical properties of machined
components will largely affect their functional performance, such
as corrosion resistance. Ghosh et al. [5] demonstrated a higher SCC
susceptibility of surface machined 304L in 5 N H2SO4 0.5 N NaCl
n
Corresponding author at: Department of Material Science, Dalarna University,
SE-79188 Falun, Sweden.
E-mail address: nzh@du.se (N. Zhou).
roughness and poor surface nish have been reported to initiate
pits, which have been suggested as precursors to cracks [6]. The
presence of strain induced martensite on the surface from ma-
chining resulted in higher SCC susceptibility of 304L austenitic
stainless steel [7]. Cracking in different patterns along and trans-
verse to the milling direction has been shown by Lyon et al. [8].
In general it is considered that SCC occurs as a result of the
interaction of three factors: a corrosive environment, a susceptible
alloy and the presence of tensile stresses [2]. However, micro-
structural effects and stress localization may also play a signicant
role. Karlsen et al. [9] demonstrated that strain heterogeneity due
to the low stacking fault energy of austenitic stainless steels pro-
moted strain localization during surface mechanical treatment,
which in turn promoted crack initiation. The improvement of SCC
resistance of 304 austenitic stainless steel by laser peening has
been demonstrated by Lu et al. [10]; they attributed this to the
generation of high-level compressive residual stress and grain
renement. Cold rolling texture was found to inuence corrosion
behavior of 304 stainless steel; the presence of close pack crys-
tallographic planes parallel to the sample surface was reported to
improve the corrosion properties [11]. Grain boundary mis-
orientation ahead of the crack tip in 316 stainless steel has been
detected by the Transmission Kikuchi diffraction (TKD) technique
[12]. Research has shown that there is a connection between in-
tergranular crack propagation and the misorientation of the grain

http://dx.doi.org/10.1016/j.msea.2016.01.078
0921-5093/& 2016 Elsevier B.V. All rights reserved.
 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059
boundaries along which the cracks propagate. [13,14]. A duplex
structure of stainless steel has generally been found to improve Cl-
SCC resistance compared to austenitic grades, although this may
depend on the actual test environment [15].
There is a range of loading methods that can be used to assess
stress corrosion cracking susceptibility. Four-point bend loading is
widely used for strip material in the elastic deformation regime.
The specimen holder design and elastic stress calculation are de-
scribed in ASTM G39 [16] and ISO 7539 [17]. However, the actual
stress in the specimen surface may deviate appreciably from the
calculated values if residual stresses are present or local plasticity
occurs. In addition, stress relaxation during exposure should be
taken into account since differences in stress relaxation with dif-
ferent loading methods and for different materials have been ob-
served to cause different corrosion behavior in the same en-
vironment [18].
When fabricating stainless steels, grinding is an important and
widely used surface nishing process. Grinding induces consider-
able plastic deformation and generates thermal energy, both of
which lead to changes in the residual stress state in the material. It
has been shown that the sum of externally applied stresses and
residual stresses can lead to crack initiation and propagation and
also demonstrated that an induced high-level of compressive re-
sidual stress from laser peening can be released during the U-bend
process [10]. However, little research has been performed to dene
the role of pure residual stresses in crack initiation and growth.
The aim of this work is to contribute to the understanding of
the role of residual stresses by studying the chloride induced
stress corrosion behavior of as-delivered and surface ground 304L
austenitic stainless steel. Specimens have been exposed both
without external loading and under different four-point bend
loads.
2. Material and methods
2.1. Material
The material investigated in this study was 304L austenitic
stainless steel with 2B surface nish supplied by Outokumpu
Stainless AB as test coupons 400 mm  150 mm  2 mm in di-
mensions. The as-delivered material had been solution annealed
(1100 C, forced air cooling and water quenched), pickled and roll
leveled. The chemical composition and main measured mechan-
ical properties perpendicular to the rolling direction at room
temperature are given in Tables 1 and 2, respectively. Fig. 1 shows
the microstructure of the material from EBSD mapping. Ferrite
measurement according to ASTM E1245 [15] showed 1.7% of ferrite
to be present in the material. For these measurements the cross-
section of the as-delivered material was etched in 40% NaOH so-
lution, using 2.5 V for 3 s, then measurements were made on 10
elds throughout the thickness at  1000 magnication.
2.2. Grinding operations
The grinding operations were conducted on a Chevalier FSG-
2A618 grinding machine; the set-up is described in detail in [19]. A
Kemper RADIX Go grinding wheel (150 mm in diameter, 50 mm in
width), which is an expanding roller made of 20 mm thick rubber,
Table 1
Chemical composition (wt%) of 304L austenitic stainless steel.
C Si Mn P S Cr Ni Nb Cu Co
0.019 0.32 1.55 0.029 0.001 18.22 8.11 0.011 0.31 0.16
51
Table 2
Mechanical properties of 304L austenitic stainless steel measured perpendicular to
the rolling direction at room temperature.
Rp0.2(MPa) Rm(MPa) Elongation (%) Hardness (HB)
230 642 54 170
was used. Grinding belts (50 mm in width, 473 mm in length) with
conventional aluminum oxide grit were mounted on the grinding
wheel and the test coupon was mounted on the grinding table.
The grinding operations were performed along the rolling direc-
tion of the material. A xed grinding speed vs=23 m/s, a xed feed
rate vw =8 m/s and a xed motor power of 600 W were used.
Grinding was rst performed for 5 min using 60# grit size abrasive
to remove the as-delivered material surface, and then followed by
2.5 min grinding with a new 60# grit size abrasive to get the nal
surface nish. No grinding lubrication was used during the op-
erations. A piezo-electric transducer-based dynamometer, Kistler
9275B, was mounted under the working table to measure the
normal force during the grinding operations. The measured nor-
mal force was 100 N in this study.
2.3. Material characterization
SEM (Scanning electron microscopy, FEG-SEM Zeiss Ultra 55)
was used to investigate the surface topography and ECCI (electron
channeling contrast imaging, Hitachi FEG-SEM SU-70) to in-
vestigate the near surface microstructure evolution. Cross-sections
of selected specimens after exposure were investigated from both
longitudinal (LD) and transversal (TD) directions and some frac-
ture surfaces were examined.
The in-depth proles of residual stresses parallel ( ) and per-
pendicular ( ) to the rolling directions were determined by X-ray
diffraction for both as-delivered and ground samples. Cr K ra-
diation was used and residual stresses were determined from the
measured diffraction peak at 2  128 for the {220} lattice planes.
The method is described in detail in [20] and the set-up used in
the current work is similar to that used in the authors' previous
work on duplex stainless steel 2304 [21]. In-situ surface stress
measurements were also made on specimens subjected to loading
in the same four-point bending xtures which were used for the
stress corrosion cracking testing. The loading was increased in
steps to levels of 10, 200, 300 and 500 MPa, calculated according
to ASTM G39 [16]. At each loading level, the specimen was kept
one hour for stress relaxation, then X-ray diffraction was used to
measure the actual surface stresses parallel to the loading direc-
tion. It should be noted that the two higher loads are above the
measured proof stress of the as delivered material and thus strictly
outside the range for which the four-point loading formula [16] is
valid. After the measurement, all specimens which were kept in
the holder at 500 MPa were heated in a furnace at 155 C for 24 h,
then allowed to cool to room temperature in the furnace. Surface
residual stresses were measured again to investigate the stress
relaxation. Surface stresses were also measured after corrosion
tests.
2.4. Stress corrosion tests
Chloride induced stress corrosion cracking susceptibility was
tested without external loading and under four-point bend load-
ing. As illustrated in Fig. 2, three types of specimens were tested.
The as-delivered specimens, cut with the long axis parallel to the
N rolling direction, are denoted AD. Grinding was performed parallel
0.071
to the rolling direction, and specimens were cut either parallel to
the rolling/grinding direction, denoted ground-RD or transverse to
52 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059
Fig. 1. Cross-section microstructure and grain orientation of 304L austenitic stainless steel as-delivered.
Fig. 2. Schematic illustration of the orientation and designation of the different
specimens tested.
rolling/grinding direction, denoted ground-TD.
The test environment was boiling magnesium chloride solution
according to ASTM G36 [22] Prior to testing all the specimen edges
were ground down using 800# grinding paper to avoid sharp
edges and specimens were then allowed to passivate in air for at
least 24 h before exposure. The specimens were exposed in a ask
connected to a water cooled condenser, and the temperature was
maintained at 155 C 71 C with the help of a thermometer in the
test solution. The rst set of tests was without external loading to
investigate to role of residual stresses. All three types of specimens
(dimension 45 mm  10 mm  2 mm) were exposed for 20 h, then
removed and checked for macro-cracks. This was done in a ste-
reomicroscope (Nikon SMZ-2T with ColorView Soft camera and
CellA ColorView Soft image software) at  1063 magnication. If
no macro-cracks were observed, the specimens were then put
back for another 20 h exposure.
In the second series of tests, a four-point bend load was applied
to specimens of dimensions 65 mm  10 mm  2 mm according to
ASTM G39 [16]. The loading direction was along the longitudinal
direction. After application of the load, each specimen was kept
one hour in air to allow possible stress relaxation before exposure.
In this case the initial test period was 24 h.
3. Results
3.1. Pre-corrosion characterization
3.1.1. Surface topography
SEM images of as-delivered and ground surface topography are
shown in Fig. 3. The as-delivered surface in Fig. 3(a) is typical for a
2B surface and shows that the pickling process during production
slightly etched the grain boundaries. For the ground specimen, as
illustrated in Fig. 3(b), surface defects such as deep grooving,
smearing, adhesive chips and indentations were found. The gen-
eration of surface defects during grinding has been described in
detail in previous work [19] and such defects are also observed
when grinding duplex stainless steels [21].
3.1.2. Residual stresses
The in-depth residual stress proles parallel ( ) and perpen-
dicular ( ) to the rolling directions as well as the full width at half
maximum (FWHM) proles of both as-delivered and ground spe-
cimens are presented in Fig. 4. Fig. 4(a) shows a low level of re-
sidual stress in the as-delivered material. Both and are close to
zero from the surface layer to the subsurface region. However, the
grinding operations generated tensile but compressive in the
surface layer as seen in Fig. 4(b). The tensile was highest in the
ground surface, up to 361 746 MPa, and dropped rapidly to
compression within a depth of around 15 mm. The compressive
showed a relative low value of 54 720 MPa in the surface layer,
but increased rapidly to reach a peak of almost 250 MPa in the
subsurface region, and then dropped gradually to zero in the bulk
material.
The full width of half maximum (FWHM) revealed broadening
of the diffraction peak, which may be considered to indicate
plastic deformation [23]. FWHM showed similar values from sur-
face to subsurface for as-delivered material. However, for the
ground specimen, a decrease of FWHM with increasing depth was
observed, which reveals a gradient of plastic deformation over
40 mm in thickness under the ground surface.
3.1.3. Surface stresses under external loading
Surface stresses measured in the as-delivered, ground-RD and
ground-TD specimens subjected to four point bending are pre-
sented in Fig. 5. For all three specimens, four loading steps of 10,
200, 300 and 500 MPa were applied. For the as-delivered material,
an additional specimen with one more loading step of 110 MPa
was measured to check the accuracy and repeatability. For the as-
delivered material the actual surface stresses are close to the cal-
culated loading in the elastic regime. Above the proof stress of the
material, which is around 230 MPa, the slope of the curve de-
creases signicantly, so that a calculated applied load of 500 MPa
gives an actual stress of only 250 MPa. It should be noted, as
mentioned earlier, that this loading level is outside the valid re-
gime for four-point loading according to ASTM G39.
The results were very different for the ground specimens (Fig. 5
(b)). Both of the curves show linear trends over the whole loading
range, indicating that work hardening has signicantly increased
the local proof stress. The actual surface stress of the ground-TD
specimen is around two thirds of the calculated load. For the
ground-RD sample, the slope is a little higher compared to the TD
direction. It is seen that as the applied stress adds on to the re-
sidual tensile stress in the rolling and grinding direction, the actual
stress is 750 MPa when a calculated loading of 500 MPa is applied.
Fig. 6 presents the measured surface stress in the loading di-
rection at 500 MPa applied loading and after heat treatment at
155 C for 24 h. The results show that stress relaxation is of the
order of around 50 MPa.
3.2. Corrosion behavior without external loading
3.2.1. Surface and in-depth morphology after exposure
Typical SEM images of the surface morphology after corrosion
 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059 53

Fig. 3. Surface topography of (a) as-delivered material, (b) ground specimen.

Fig. 4. In-depth residual stresses and full width at half maximum proles of (a) as-delivered material, (b) ground specimen. Positive values denote tensile stresses and
negative compressive stresses.

testing are shown in Fig. 7. Pitting was observed on all specimens.

The pits were small and the density was low. Micro-cracking took
place in all ground specimens even in the absence of any external
loading (Fig. 7(b)). Micro-cracks on the ground surfaces exhibited
extensive branching and were primarily oriented perpendicular to
the grinding marks i.e. perpendicular to the direction with the
highest tensile residual stress. However, in the case of as-delivered
specimens, there is no evidence of micro-cracks.

3.2.2. Cross-section investigation after exposure

By using the ECCI technique, diffraction contrast images can be
obtained to analyze deformation and damage of the crystalline
material [24]. Images at different magnications showing typical
cross-section microstructures of the ground specimens after ex-
Fig. 6. Stress relaxation in four-point bend specimens after heat treatment at
posure without external loading are presented in Fig. 8. It can be 155 C for 24 h for as-delivered and ground specimens.
clearly seen that the grinding operation generated a heavily

Fig. 5. Measured surface stresses in the loading direction for four-point bending of (a) as-delivered material, (b) ground specimens.
54 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059

Fig. 7. Surface morphology after exposure without external loading: (a) as-delivered specimen, (b) ground-RD specimen.

deformed surface layer comprised of fragmented grains and dis-
location sub-cells only a few microns in thickness. Below this layer,
densely populated slip bands with multiple orientations were
observed. Both the ground-RD and ground-TD specimens show
similar features from the cross-section investigations. As illu-
strated in Fig. 8(a), micro-cracks in the absence of external loading
appeared mainly perpendicular to the grinding marks i.e. per-
pendicular to the direction of highest residual tensile stress. The
cracks initiated from the ground surface and ranged in length from
less than 1 mm up to more than 10 mm. The micro-cracks were thus
largely within the highly deformed surface layer. On the other
hand, in the section parallel to the grinding marks (Fig. 8(b)), only
small rather blunt points of attack were seen; these had not de-
veloped into cracks. The results agree well with the surface mor-
phology investigation. Detailed microstructural characterization at
higher magnication revealed that both intergranular micro-
cracks (Fig. 8(c)) and transgranular micro-cracks (Fig. 8(d)) were
present. Some branching occurred (Fig. 8(d)) and cracks could run
parallel to and across deformation slip bands.
3.3. Corrosion behavior with four-point bend loading
3.3.1. Macro-crack examination
Macro-cracks developed in some specimens exposed with ex-
ternal loading and could result in sample fracture. Macro-cracks
are dened in this study as those that can be observed by stereo
microscopy with highest magnication  63. Table 3 gives a
summary of the macro-crack examination from the corrosion test
under different four-point bend loading values as well as without
external loading. No macro-cracking occurred during exposure
without external loading regardless of surface conditions. How-
ever for specimens under four-point bending, one out of three as-
delivered specimens loaded to 50 MPa was cracked through
thickness after exposure in boiling MgCl2 for 24 h. With increasing
the applied loading up to 110, 200 and 300 MPa respectively, all
the exposed as-delivered specimens cracked. For the ground-RD
specimens, large cracks were observed on both specimens with
50 MPa or 300 MPa loading. In the case of ground-TD specimens
no macro-cracks were seen at applied load levels of 50 MPa or
110 MPa.

Fig. 8. Cross-section microstructures after exposure without external loading: (a) ground-RD specimen sectioned parallel to the rolling/grinding direction, (b) ground-RD
specimen sectioned perpendicular to rolling/grinding, (c) ground-RD specimen showing intergranular micro-crack, (d) ground-RD specimen showing transgranular micro-
crack and multi-branched micro-crack.
 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059 55

Table 3
Extent of micro- and macroscopic cracking after exposure with four-point bend loading. The measured surface stresses from Figs. 4 to 5 are also included for comparison.

Specimen Applied four-point bend Measured (or interpolated) sur- Exposure time No. of specimens No. of specimens with Presence of micro-
loading (MPa) face stress (MPa) tested macro-cracks cracks

As-delivered Without external loading 5 20 h 20 h 2 0 No

Ground-RD 360 3 0 Yes
Ground-TD  54 3 0 Yes
As-delivered 50 (20), (50) 24 h 3 1 No
110 100 2 2 No
200 126, 166 2 2 No
300 177, 202 2 2 No
Ground-RD 50 (400) 2 2 Yes
300 607 2 2 Yes
Ground-TD 50 (35) 2 0 Yes
110 (70) 2 0 Yes

3.3.2. Surface morphology after exposure
Initial examination of the cracked surfaces was performed by
stereo microscopy. When cracking occurred, there were usually
multiple cracks, with one major crack extending nearly through
the specimen. The cracks tended to run parallel to each other, and
were all perpendicular to the loading direction.
Detailed characterization of all the three types of specimens
after testing at 50 MPa four-point bend loading is shown by the
SEM micrographs in Fig. 9. The macro-cracks were wide and ex-
hibited multiple branching (Fig. 9(a) and (c)). Pitting was observed
in varying degrees for all specimens. Even in the absence of macro-
cracks, large pits were found, as exemplied by the as-delivered
specimen shown in Fig. 9(b). Pits were also seen on the ground
surfaces and showed some tendency to follow the micro-cracks.
Cracks were sometimes seen to extend from pits, indicating that
pits may be precursors to cracks. Similar to the corrosion tests
without external loading, micro-cracks with extensive branching
were also found on the exposed surfaces of all ground specimens
regardless of loading or the occurrence of macro-cracks. Micro-
cracks were primarily oriented perpendicular to the grinding
marks. This applied even for the ground-TD specimens, which
means that the residual stress effect outweighed the effect of the
applied load and the possible notch effect from the grinding
marks.
3.3.3. Cross-section investigation after exposure
Cross-sections parallel to the loading direction were examined
for all the cracked specimens after exposure. Fig. 10 presents SEM
images of two specimens as examples: the AD and ground-RD
specimens with 50 MPa applied load. These show that the macro-
crack path was mainly branched transgranular, in good agreement
with the fracture surface investigation (see below). Pits were
evident on the surface and macro-cracks were always associated
with such pits, i.e. always initiated and propagated from the pits.
Micro-cracks were also observed to initiate from the surface and
have penetration depths of up to 10 mm, but these were not nor-
mally associated with pits (Fig. 10(b)). No micro-cracking was
observed in AD cross-section (Fig. 10(a)).
Cross-sections both parallel and perpendicular to the loading
directions of all the ground specimens after exposure under

Fig. 9. Surface morphology after exposure with 50 MPa four-point bend loading: (a) as-delivered cracked specimen, (b) as-delivered uncracked specimen, (c) ground-RD
cracked specimen, (d) ground-TD uncracked specimen. The loading direction is horizontal in all cases.
56 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059

Fig. 10. Cross-section microstructures showing stress corrosion cracking after exposure with 50 MPa four-point bend loading: (a) as-delivered specimen sectioned in the
longitudinal direction, (b) ground-RD specimen sectioned in the longitudinal direction.

Fig. 11. Cross-section microstructures after exposure with 50 MPa four-point bend loading showing: (a) ground-RD specimen parallel to rolling/grinding direction,
(b) ground-TD specimen perpendicular to rolling/grinding direction, (c) surface pit and micro-cracks in ground-RD specimen, (d) surface pit and micro-cracks in ground-TD
specimen.

Fig. 12. Fracture surfaces after exposure: (a) as-delivered specimen under 50 MPa loading, (b) ground-RD specimen under 50 MPa loading.

different applied loads were examined by ECCI. Images of two agreement with the surface morphology results. For the ground-
specimens are illustrated in Fig. 11 as examples. A high density of RD specimens, 50 MPa four-point bend loading signicantly in-
pits and micro-cracks was observed for all the specimens, in creased the density and size of the pits. The penetration depth of
 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059
micro-cracks also obviously increased, especially for cracks per-
pendicular to the loading/grinding direction (Fig. 11a), when
comparing with the same specimen exposed without external
loading. For the ground-TD specimen, the same load also sig-
nicantly increased the penetration depth and density of micro-
cracks perpendicular to the loading direction i.e. parallel to the
grinding direction (Fig. 11(b)). However the change was small for
micro-cracks parallel to the loading direction. Higher magnica-
tion characterization revealed that multiple cracks often origi-
nated from a single pit (Fig. 11 (c) and (d)), which also agrees with
the exposed surface observation. Both transgranular and inter-
granular micro-cracks were observed to be associated with pits
(Fig. 11 (c)) and these could run parallel to or across the de-
formation slip bands (Fig. 11(d)).
3.3.4. Fracture surface investigation
Fig. 12 presents SEM images showing fracture surfaces of both
as-delivered and ground-RD specimens which cracked at 50 MPa
applied stress. The fracture appearance of both specimens shows
typical cleavage fracture which is predominantly transgranular,
although there are also some local indications of intergranular
cracking. Some indications of crack branching are seen for both of
the specimens.
3.4. Stress relaxation after exposure
Surface stresses of ground specimens before and after exposure
under different loading conditions were measured to correlate the
SCC behavior and residual stresses; the results are presented in
Fig. 13. The grinding operations generated tensile residual stresses
up to more than 350 MPa parallel to the grinding direction and
compressive residual stresses in the perpendicular direction. For
the ground-RD specimen (Fig. 13(a)), after 40 h exposure without
applying any external loading, surface tensile stresses parallel to
the grinding marks signicantly reduced to below 100 MPa; while
perpendicular to the grinding marks, compressive stresses in-
creased slightly. These effects can be directly related to the for-
mation of micro-cracks which relax the surface tensile stress. After
exposure at 50 MPa applied load, surface tensile residual stresses
reduced even more, to below 50 MPa, this is attributable to the
formation of both micro- and macro-cracks. The change in the
perpendicular direction was again small. For 300 MPa loading,
surface stress reduced to zero in the loading direction. In the case
of ground-TD specimen (Fig. 13(b), the surface stress relaxation
due to exposure without external loading was similar to the
ground-RD specimen. The inuence of applied loading up to
110 MPa on surface stress relaxation was relatively small, and it
Fig. 13. Measured surface residual stress of ground specimens parallel and perpendicular to rolling and grinding directions before and after exposure: (a) ground-RD
specimen, (b) ground-TD specimen.
57
may be recalled that this specimen exhibited no macro-cracking.
In-depth residual stress prole of a ground-RD specimen before
and after exposure in the absence of external loading is presented
in Fig. 14. Residual stresses were measured both parallel and
perpendicular to rolling/grinding directions of the specimen. As
shown in the gure, the tensile component reduced dramatically
after exposure from surface to sub-surface until reaching zero at
the depth where nearly all the micro-cracks stopped. The change
of compressive component showed small, in-depth residual
stresses showed similar values before and after exposure.
In-depth surface morphology (Fig. 14) was also characterized of
this specimen with different distances from the original surface.
The penetration depths of micro-cracks were very uneven. Some
of them disappeared after 2 mm of surface has been polished away,
while some penetrated to a depth more than 10 mm from surface.
Very few micro-cracks can be observed at 13 mm electrolytic pol-
ishing depth. The results agree with the cross-section observation.
4. Discussion
4.1. Residual stress distribution
Residual stresses for the as-delivered material are close to zero,
while grinding operations generated massive residual stresses in
the surface and sub-surface layers of the steel. During grinding,
thermally and mechanically induced residual stresses may be
produced simultaneously; the relative signicance varies from one
process to another [25]. Heat is generated from the interaction
between the abrasive grit and the workpiece material during
grinding operations. Due to the low thermal conductivity of 304L
stainless steel, a temperature gradient is formed from surface to
the bulk. During the cooling period, contraction of the surface
layer is hindered by the bulk thus resulting in surface tension and
subsurface compression [25,26]. However, in the present case
tensile residual stresses parallel to the grinding direction and
compressive residual stresses perpendicular to the grinding di-
rection were observed. This measured anisotropic surface residual
stress can be attributed to the anisotropic plastic deformation of
the ground surface layer, and indicates that residual stresses in-
duced by mechanical effects dominate over thermal effects in this
study. The surface layer experienced compressive plastic de-
formation in the grinding direction and tensile deformation in the
transverse direction. After the grinding zone moved away, the
constraint by the material beneath surface resulted in tensile but
compressive in the surface layer [20,27]. Such anisotropic re-
sidual stress distributions have also been observed in previous
58 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059
Fig. 14. In-depth residual stress parallel and perpendicular to the rolling/grinding
directions of ground-RD specimen before and after exposure without external
loading and corresponding micrographs showing the appearance of the micro-
cracks at each depth.
work when grinding duplex stainless steel 2304 [21].
4.2. Corrosion behavior without external loading
The micro-cracks and their pattern on the ground surfaces after
exposure are one of the most interesting observations in this
study. Extensive stress corrosion micro-cracks were observed on
the ground surfaces even in the absence of any external loading,
while the as-delivered material showed no such cracking. Similar
crack patterns have also been observed by Lyon et al. on milled 316
surfaces [8]. It has also been shown in other work that surface
failure often occurs due to surface tensile residual stresses gen-
erated in metallic materials [2]. Compressive residual stress on the
surface can delay crack initiation, and compressive residual
stresses at depth can slow down the growth of cracks from the
surface [10]. In the present study, high levels of tensile residual
stresses up to 350 MPa were measured parallel to the grinding
direction in the surface layer, with compressive stresses in the
perpendicular direction. Consequently the micro-cracks tended to
initiate normal to the grinding marks. Both the in-depth surface
morphology characterization and the cross-section investigation
showed the micro-cracks perpendicular to the grinding direction
were more numerous and longer than those parallel to the
grinding marks. This strongly indicates that the tensile residual
stresses in the surface layer make austenitic stainless steel sus-
ceptible to SCC in the presence of chlorides even without any
external loading, whereas compressive residual stress can retard
the initiation of cracks. The majority of the micro-cracks arrested
after penetrating 1015 mm through the highly deformed ground
surface layer. This correlates well to the position at which the
residual stresses shift from tension to compression. A threshold
stress is required to initiate and maintain the propagation of SCC
[28]. Results of surface residual stress measurement after exposure
showed that the formation of micro-cracks caused a signicant
release of the surface residual stress.
4.3. Corrosion behavior with four-point bend loading
The in-situ X-ray diffraction measurements on as-delivered
specimens and ground specimens demonstrated that the actual
stress in the surface of the specimens deviated from the values
calculated according to ASTM G39 [16] and were strongly affected
by the surface preparation. The repeated measurement on the as-
delivered material indicated good accuracy and repeatability of the
results. The actual loading corresponded reasonably well with the
calculated values from ASTM G39 in the elastic regime, although
the measurements showed an actual stress of 126/166 MPa when
200 MPa was applied. Above the proof stress the slope of the curve
dropped dramatically, so a calculated applied stress of 300 MPa
gave an actual value below 200 MPa. This serves to underline the
point that four point bending should never be used in the plastic
regime.
The in-situ stress measurements under four point loading
showed a different trend for ground specimens. The surface layer
was highly deformed by the grinding operation, which was clearly
shown from the cross-section ECC images with fragmented grain
structures and deformation slip bands in the surface layer. Due to
strain hardening in this layer, the measured surface stress ap-
peared to increase nearly linear with increasing load even up to
500 MPa. The actual surface stress in such specimens with residual
stresses and a strength gradient near the surface depends on in-
teractions between the applied and residual stresses as well as the
strength gradient in the specimen [29]. For the ground-RD speci-
men, the surface tensile residual stress along the loading direction
resulted in a high surface stress, for example 750 MPa for loading
at 500 MPa level. On the other hand, the ground-TD specimen with
a low surface residual stress parallel to the applied stress showed
initially similar surface stress as the as-delivered specimen but
owing to its higher surface strength, the linear behavior remained
up to loading of 500 MPa. A detailed analysis of interactions be-
tween the stresses and the effect of the strength gradient is an
avenue worth further investigation.
Stress relaxation was found to be low for all three types of
specimens under 500 MPa four-point bend loading after annealing
at 155 C for 24 h: around 50 MPa. The main stress relaxation was
due to the formation of micro- or macro-cracks.
The crack path was mainly transgranular in this study, although
there were some local areas of intergranular cracking. The macro-
cracks followed a general path which was normal to the loading
stress. The SCC susceptibility increased considerably with in-
creasing four-point bend loading and the data in Table 3 indicated
that there is a threshold stress of around 50 MPa for macroscopic
cracking.
Pits were observed on all the exposed specimens to varying
degrees. When characterizing pitting and cracking behavior, there
is always a question as to whether pits formed after cracking, or
whether cracking initiated from pits. Many works have demon-
strated that pits can act as precursors to cracking [8,30,6]. The
explanation is usually that the cause is a combination of stress
concentration and a more aggressive environment in the pits [2].
In the present study, all macro-cracks were observed to be asso-
ciated with pits, although there were also pits without any related
cracks. This indicates that pits form before macro-cracks and act as
precursors to macro-cracking. However, the behavior of the micro-
cracks was different. Extensive micro-cracks appeared on the
specimens that had been ground and could be both with and
without associated pits. This indicates that tensile residual stress
in the surface layer was the main driving force for the initiation of
micro-cracks and pits tended to grow from these micro-cracks. In
the case of ground-RD specimens, these pits appeared to grow
together along the micro-cracks in the perpendicular direction to
the grinding marks and led to the macro-crack initiation. More-
over, the micro-cracks in both directions of all ground specimens
with four-point bend loading were longer that those in absence of
external loading, especially in the direction perpendicular to
grinding marks, indicating that applied tensile stresses promote
micro-crack propagation.
The macro-cracking showed that the ground-RD specimens
were more susceptible to SCC than the as-delivered specimens.
Surface nish, surface deformation and microstructure can all in-
uence the SCC behavior; however, the detrimental role of re-
sidual tensile stress from grinding in combination with an applied
 N. Zhou et al. / Materials Science & Engineering A 658 (2016) 5059
stress is dominant here. In contrast, the improvement of SCC re-
sistance of ground-TD specimens was also clear; although the in-
duced compressive residual stresses were entirely released during
loading and were then converted into a state of tension, much
higher level of compressive residual stresses beneath the ground
surface compensated for the surface tension and effectively re-
tarded the appearance of macro-cracks. The results suggest the
idea that grinding transverse to the main stress direction in a
construction could possibly be used to decrease the cracking risk.
5. Conclusions
The effect of surface grinding on chloride induced stress cor-
rosion cracking of austenitic stainless steel 304L has been in-
vestigated. The following conclusions can be drawn:
 Grinding generated tensile residual stresses parallel to the
grinding direction ( ) but compressive residual stresses per-
pendicular to the grinding direction ( ) in the surface layer.
Beneath the ground surface, a layer of compressive stresses in
both directions was formed with much higher values in the
perpendicular direction. The residual stress distribution ob-
served in this study indicated that anisotropic mechanical ef-
fects dominated over isotropic thermal effects from grinding.
 Stress measurements on four-point bend loaded specimens
demonstrated that the actual loading may deviate appreciably
from that calculated according to the formula in ASTM G39. For
annealed material with low residual stresses the formula gave a
reasonable estimate of the applied stress up to the proof stress.
For surface ground material there was a linear relationship up to
much higher loads but the absolute value was strongly affected
by residual stresses from grinding.
 Surface tensile residual stresses were found to be the main
factor causing the initiation of micro-cracks on ground surfaces
during exposure with or without an externally applied load.
Crack arrest occurred when micro-cracks grew into a region 10
15 mm below the surface with low or no tensile residual stresses.
 Macroscopic cracking leading to nal failure only occurred un-
der an applied load and there appeared to be a threshold at load
of around 50 MPa. A residual tensile stress in the grinding di-
rection increased the susceptibility to chloride-induced SCC
while grinding perpendicular to the applied loading direction
retarded cracking. It is therefore suggested that grinding
transverse to the main stress direction in a construction could
possibly be used to decrease the cracking risk.
 Pits tended to initiate at micro-cracks on the surface, and
macro-cracks were always associated with pits. This indicates
that pits formed before macro-cracks and acted as precursors to
macroscopic crack development.
Acknowledgment
This work was performed within the Swedish Steel Industry
Graduate School with nancial support from Outokumpu Stainless
Research Foundation, Region Dalarna, Region Gvleborg, Lns-
styrelsen Gvleborg, Jernkontoret, Sandviken Kummun and
Hgskolan Dalarna. The assistance with part of the sample pre-
paration work by Ulf Modin at Hgskolan Dalarna is also appre-
ciated. The authors are grateful to Timo Pittulainen at Outokumpu
Stainless AB for providing the test materials and the material data.
References
[1] R. Pettersson and E. Johansson, Stress corrosion resistance of duplex grades, in
59
Duplex stainless steel world conference, Beaune, 2010.
[2] D.A. Jones, Principles and Prevention of Corrosion, Pearson Education, US,
1996.
[3] S. Ghosh, V. Kain, Effect of surface machining and cold working on the ambient
temperature chloride stress corrosion cracking susceptibility of AISI 304L
stainless steel, Mater. Sci. Eng. A 527 (2010) 679683.
[4] W. Jin, S. Yang, H. Kokawa, Z. Wang, Y.S. Sato, Improvement of intergranular
stress corrosion crack susceptibility of austenite stainless steel through grain
boundary engineering, J. Mater. Sci. Technol. 23 (2007) 785789.
[5] S. Ghosh, V.P.S. Rana, V. Kain, V. Mittal, S. Baveja, Role of residual stresses
induced by industrial fabrication on stress corrosion cracking susceptibility of
austenitic stainless steel, Mater. Des. 32 (2011) 38233831.
[6] A. Turnbull, K. Mingard, J. Lord, B. Roebuck, D. Tice, K. Mottershead,
N. Fairweather, A. Bradbury, Sensitivity of stress corrosion cracking of stainless
steel to surface machining and grinding procedure, Corros. Sci. 53 (2011)
33983415.
[7] S. Ghosh, V. Kain, Microstructural changes in AISI 304L stainless steel due to
surface machining: effect on its susceptibility to chloride stress corrosion
cracking, J. Nucl. Mater. 403 (2010) 6267.
[8] K. Lyon, T. Marrow, S. Lyon, Inuence of milling on the development of stress
corrosion cracks in austenitic stainless steel, J. Mater. Process. Technol. 218
(2015) 3237.
[9] W. Karlsen, G. Diego, B. Devrient, Localized deformation as a key precursor to
initiate of intergranular stress corrosion cracking of austenitic stainless steels
employed in nuclear power plants, J. Nucl. Mater. 406 (2010) 138151.
[10] J. Lu, K. Luo, X. Cheng, J. Hu, F. Dai, H. Qi, L. Zhang, J. Zhong, Q. Wang, Y. Zhang,
Effects of laser peening on stress corrosion cracking (SCC) of ANSI 304 aus-
tenitic stainless steel, Corrosion Science 60 (2012) 145152.
[11] B. Kumar, R. Singh, B. Mahato, P. De, N. Bandyopadhyay, D. Bhattacharya, Effect
of texture on corrosion behavior of AISI 304L stainless steel, Mater. Charact. 54
(2005) 141147.
[12] M. Meisnar, A. Vilalta-Clemente, A. Gholinia, M. Moody, A.J. Wilkinson,
N. Huin, S. Lozano-Perez, Using transmission Kikuchi diffraction to study in-
tergranular stress corrosion cracking in type 316 stainless steels, Micron 75
(2015) 110.
[13] S.-l Baik, M. Olszta, S. Bruemmer, D.N. Seidman, Grain-boundary structure and
segregation behavior in a nickel-base stainless ally, Scr. Mater. 66 (10) (2012)
809812.
[14] S.M. Bruemmer, M.J. Olszta, M.B. Toloczko, L.E. Thomas, Linking grain bound-
ary microstructure to stress corrosion cracking of cold rolled alloy 690 in
PWRprimary water, Corrosion (2012) 95129527.
[15] E. Johansson, T. Prosek, Stress corrosion cracking properties of UNS S32101- a
new duplex stainless steel with low nickel content, in: Proceedings of the
Corrosin 2007 Conference & Expo, 2007.
[16] ASTM, G39-99, Standard Practice for Preparation and Use of Bent-beam Stress-
corrosion Test Specimens, 2011.
[17] ISO, 7539, Corrosion of Metals and Alloys Stress Corrosion Testing, 1995.
[18] U. Kiviskk, G. Chai, Inuence of test method and relaxation on the result from
stress corrosion cracking tests of stainless steels in dilute neutral chlorides,
Corrosion 59 (2003) 828835.
[19] N. Zhou, R.L. Peng, R. Pettersson, Surface characterization of austenitic stain-
less steel 304L after different grinding operations, J. Mater. Process. Technol.
(2015), under review.
[20] I. Noyan, J. Cohen, Residual Stress Measurement by Diffraction and Inter-
pretation, Springer-Verlag New York Inc, New York City, United States, 1987.
[21] N. Zhou, R. Lin Peng, R. Pettersson, Surface integrity of 2304 duplex stainless
steel after different grinding operations, J. Mater. Process. Technol. 229 (2016)
294304.
[22] ASTM, G36-94, Standard Practice for Evaluating Stress-Corrosion-Cracking
Resistance of Metals Aned Alloys in a Boiling Magnesium Chloride Solution,
Reapproved 2006.
[23] V. Roy, B. Nahak, M.Z.K. Yusufzai, M. Vashista, Assessment of plastic de-
formation upon grinding using X-ray diffraction proles, Int. J. Eng. Res. 2 (2)
(2013) 119124.
[24] S. Johansson, J. Moverare, R. Peng, Recent applications of scanning electron
microscopy, Pract. Metallogr. 50 (2013) 810820.
[25] J.P. Davim, Surface Intergrity in Machining, Springer London Ltd, London,
2010.
[26] N.B. Fredj, H. Sidhom, C. Braham, Ground surface improvement of the auste-
nitic stainless steel AISI 304 using cryogenic cooling, Surf. Coat. Technol. 200
(2006) 48464860.
[27] G. Guo, Z. Liu, X. Cai, Q. An, M. Chen, Investigation of surface integrity in
conventional grinding of Ti6Al4V, Adv. Mater. Res. 126128 (2010) 899904.
[28] P. Marcus, Corrosion Mechanisms in Theory and Practice, CRC Press Inc, Boca
Raton, 2012.
[29] R. Lin Peng, J. Gibmeier, G. Chai, S. Johansson, Load Partitioning in a Duplex
Stainless Steel With Surface Strength Gradient and Residual Stresses, in:
JCPDS-International centre for diffraction data, 2009.
[30] G. Hinds, L. Wickstrm, K. Mingard, A. Turnbull, Impact of surface condition on
sulphide stress corrosion cracking of 316L stainless steel, Corros. Sci. 71 (2013)
4352.