applied

sciences
Article
Pitting Corrosion in AISI 304 Rolled Stainless Steel
Welding at Different Deformation Levels
Francisco-Javier Cárcel-Carrasco 1 , Manuel Pascual-Guillamón 1 , Lorenzo Solano García 2, *,
Fidel Salas Vicente 1 and Miguel-Angel Pérez-Puig 1
1 ITM, Universitat Politècnica de València, 46022 Valencia, Spain
2 Departamento de Ingeniería Mecánica y de Materiales, Universitat Politècnica de València,
46022 Valencia, Spain
* Correspondence: lsolano@mcm.upv.es; Tel.: +34-963-87-7000 (ext. 76273); Fax: +34-963-87-7627




Received: 12 July 2019; Accepted: 7 August 2019; Published: 9 August 2019


Abstract: This paper analyzes pitting corrosion at the weld zone and at the heat affected zone
(HAZ) in AISI 304 rolled stainless steel welds. As the aforementioned material is one of the most
frequently used types of stainless steel, it is needful to be aware of the mechanisms that lead to
its deterioration, like corrosion, since it can cause failures or malfunction in a wide variety of
products and facilities. For the experimental tests 1.5 mm thick AISI 304 stainless steel plates were
welded and rolled to different thicknesses and after, the samples were subjected to mechanical and
corrosion tests and to a micrograph study. Deformation stresses and other intrinsic metallurgic and
physic-chemical transformations that occur during cold rolling and welding, and that are key factors
in the anti-corrosion behavior of AISI 304 rolled stainless steel, have been observed and analyzed.
A correlation has been found between cold work levels in test samples and number of pits after
corrosion tests.

Keywords: pitting corrosion; welding; cold rolling; deformation stress; AISI 304; AISI 308L

1. Introduction
The objective of this study is to analyze the resistance of AISI 304 welds to pitting corrosion when
they have been subjected to different levels of cold rolling, as well as to establish a correlation between
the pitting corrosion and cold rolling deformation level.
The pitting corrosion, initiated at certain points of the surface due to the non-uniformity of the
passive layer, is a localized redox (reduction-oxidation) process that occurs inside small pits on the
surface of passivated metals in aqueous media. This kind of reaction requires the balancing of both
the reduction and oxidation half-reactions. The anodic reaction that takes place inside the pit leads to
the dissolution of iron (Fe → Fe2+ + 2e− ) while the cathodic reaction, that makes use of the electrons
liberated by the anodic reaction, leads to the apparition of hydroxide (1/2O2 + H2 O + 2e− → 2(OH− )).
As inside the pit, the electrolyte solution becomes positively charged due to the presence of Fe2+ ions,
the anionic species (Cl− ) in the electrolyte are attracted there, increasing the acidity inside the pit and
accelerating the corrosion process according to the reactions:

FeCl3 → Fe3+ + 3Cl− (outside the pit)

Fe3+ + 3(OH)− → Fe(OH)3 (outside the pit)
Fe2+ + 2Cl− → FeCl2 (at the pit)
FeCl2 + 2H2 O → Fe(OH)2 + 2HCl (at the pit)

Appl. Sci. 2019, 9, 3265; doi:10.3390/app9163265 www.mdpi.com/journal/applsci

Appl. Sci. 2019, 9, 3265 2 of 12

Furthermore, the solid Fe(OH)3 deposited around the pit increases the separation of the inside
of the pit from the rest of the electrolyte. The presence of chemical species that provide a high
concentration of Cl− in the aqueous media is needed to accelerate the process of corrosion in the pit.
AISI 304 stainless steel is widely used in the manufacturing of both industrial and domestic
products, mainly due to the combination of characteristics that presents: Good mechanical properties
(high strength, ductility and malleability); non-magnetic behavior; weldability; resistance to corrosion
and low cost [1–4]. It is used in applications that entail a high stress level and/or exposure to corrosive
atmospheres, like in nuclear power plants [5,6], marine environments [7,8] or in large facilities [9].
Particularly, AISI 304 rolled stainless steel is one of the most frequently used types of stainless steel,
whereby it is needful to be aware of the mechanisms that lead to its deterioration in order to foresee,
restrict and/or quantify the economic costs that could be derived. Corrosion is one of the key factors
to consider, as it can cause failures or malfunction in all types of products and facilities. Specially,
when they get in contact with corrosive agents or when they are used in conditions or participate in
processes that bring on corrosion [8], like welding and cold forming.
The anti-corrosion behavior of welded stainless steels has been studied previously [10]. AISI 304
stainless steel can be welded by almost all the common welding techniques [11]. In arc welding the
use of a low carbon content stainless steel as a filler rod reduces chromium carbide, which improves
corrosion resistance [7,12]. However, corrosion resistance can be affected when stainless steel is
subjected to cold rolling [13,14]. The friction and compression forces under conditions of dynamic
plastic deformation cause the material fibers to stretch while its stress level rises and its hardness
increases [15]. Beyond a certain level of deformation different types of defects and even failure can
occur. If the process is under control these defects can be avoided, but the relieve of internal stresses
requires an annealing treatment [16].
Alike, when materials obtained by cold rolling are welded, the stress state changes due to the effect
of heat and the apparition of new stresses during the cooling of the weld, especially if deformation is
impeded. These welding stresses depend on the energy applied and the heat transmission conditions
during the welding process [17]. Cold rolling and welding are part of various manufacturing processes.
So, the combined effect of both in the stresses increment, and its influence in corrosion, can be present
in many manufactured products.
The effect of the residual stresses generated during products manufacturing of stainless steel on
the stress corrosion cracking susceptibility is presented by [18]. Other works listed below focused
on the pitting corrosion, the factors that cause it and their effects: In [19] a summary of the effects of
possible factors in the pitting corrosion of metals is given; in [20] cold working was discussed as one
factor on the mechanism and rate of pitting corrosion; in [21] the pitting generation caused by applied
stress has been studied; in [22] an overview of the critical factors influencing the pitting corrosion of
metals is provided; in [23] a method of evaluating strength reduction due to the pitting corrosion is
established; in [24] a quantitative analysis of the effect of Type I residual stresses on the occurrence of
pitting and stress corrosion is investigated; in [25] the effects of the micro-plasma arc welding technique
on the pitting corrosion of different zones of an AISI 316L stainless steel were studied; in [12] the effect
of low intensity X-rays ionizing radiation on TIG-welds of AISI 304 stainless steel using AISI 316L as
filler rods is analysed.
In this work, a batch of welded samples of AISI 304 stainless steel were subjected to different
levels of cold work to change the shape of grains, create residual stresses and damage the surface.
The influence of those changes in the pitting corrosion resistance of the welds was evaluated by the
immersion of the samples in a FeCl3 solution according to a standardized test and quantified by the
pits number [8,26–29]; while deformation levels were measured as the thickness reduction of the metal
samples (cold work level). A mathematical relation between the cold work level and the number of
pits is proposed for the tested samples.
Appl. Sci. 2019, 9, x FOR PEER REVIEW
3265 33 of 13
of 12

traction and stamping. The filler metal was low-carbon ER AISI 308L, which reduces the formation
2.
of Materials
chromiumand Experimental
carbide Procedures
in the grain boundary during welding and is recommended for TIG or MIG
(metal inert gas) welding of the AISI 304 steel. The AISI 308L has good corrosion resistance, is non-
2.1. Characteristics of Materials Used
magnetic, and is principally used in the chemical industry and food applications. Its composition is
The base
also shown in material
Table 1. of the welded joint (AISI 304), whose chemical composition is given in Table 1,
is a non-magnetic weldable austenitic stainless steel with good mechanical characteristics, highly
resistant Table 1. Chemical
to corrosion, composition
which does notof harden
AISI 304in
and ER AISI
heat 308 L base
treatments andand filler deformable
easily stainless steels.
by rolling,
traction and stamping. The filler metal was low-carbon ER AISI 308L, which reduces the formation of
Material %C %Si %Mn %Cr %Ni %Mo %Fe
chromium carbide in the grain boundary during welding and is recommended for TIG or MIG (metal
AISI 304 0.07 1 2 19 11 - Bal.
inert gas) welding of the AISI 304 steel. The AISI 308L has good corrosion resistance, is non-magnetic,
ER AISI used
and is principally 308L in the0.02
chemical 0.38 1.90 food 19.80
industry and 9.8 Its composition
applications. 0.19 Bal.
is also shown
in Table 1.
2.2. Tests Description
Table 1. Chemical composition of AISI 304 and ER AISI 308 L base and filler stainless steels.
2.2.1. Sample Preparation
Material %C %Si %Mn %Cr %Ni %Mo %Fe
Welding was carried
AISI 304 out on a horizontal
0.07 1 plane
2 in an inert
19 argon atmosphere
11 -and employing
Bal. non-
consumable tungsten-thorium
ER AISI 308L 0.02 alloy electrode.
0.38 The
1.90 welding
19.80parameters9.8 were: Gun
0.19 nozzle exit
Bal. rate of
11 dm /min, current 48 A, applied bias from 10 to 12 V, travel rate of 50 mm/min, torch inclination
3

angle
2.2. from
Tests 70° to 80° and filler rod inclination angle of 15°.
Description
Stainless steel experiments more heat deformation than other carbon steels or steel alloys. So, to
2.2.1.
avoid Sample
significantPreparation
deformation during the welding process, the plates were fixed until they returned
to theWelding was carried outHowever,
ambient temperature. on a horizontalthe undesired
plane in effect of argon
an inert a smallatmosphere
residual stress due to the
and employing
deformation restriction
non-consumable during cooling
tungsten-thorium alloyiselectrode.
expectedThe [30].welding parameters were: Gun nozzle exit rate
of 11 dm /min, current 48 A, applied bias from 10 tosteel
The 3welds were carried out on twelve AISI 304 12 V,plates
travelmeasuring 200 mm intorch
rate of 50 mm/min, length, 100 mm
inclination
in width, and ◦1.5 mm ◦ thick. Once welded, the
angle from 70 to 80 and filler rod inclination angle of 15 . plates were ◦cut perpendicularly to the weld bead at 20
mm intervals
Stainless to obtain
steel 10 samples
experiments morefrom heateach plate; 60 samples
deformation in total
than other measuring
carbon steels or100steel
mmalloys.
in length,
So,
20 mm in width, and 1.5 mm thick (see Figure 1). The joints were smoothed and
to avoid significant deformation during the welding process, the plates were fixed until they returned polished, removing
surface
to irregularities
the ambient to obtaining
temperature. the same
However, thickness
the undesired as the original
effect plates.residual stress due to the
of a small
These samples
deformation were
restriction cold rolled
during cooling toisobtain five [30].
expected different thickness batches: 12 samples of 1.5 mm
thick,The
12 welds
samples were carried out on twelve AISI 304 1steel
of 1.25 mm thick, 12 samples of mmplates
thick,measuring
12 samples200 of mm
0.75 inmm thick100
length, andmm12
samples
in width,ofand 0.651.5
mm mm thick.
thick.The samples
Once welded,thickness of each
the plates werebatch
cut isperpendicularly
expressed as “e” toin Figure
the weld1.bead
Those
at
values correspond to cold work percentages of 0%, 17%, 33%, 50% and 57%,
20 mm intervals to obtain 10 samples from each plate; 60 samples in total measuring 100 mm in length,respectively.
20 mm Subsequently,
in width, and the1.5samples
mm thickselected for corrosion
(see Figure 1). Thetests
jointswere
werecutsmoothed
to 40 mmand in length, leaving
polished, welds
removing
approximately
surface in the to
irregularities center (Figure
obtaining the1).same thickness as the original plates.

Figure 1. Samples preparation for tests: Number of samples (in brackets), samples dimensions (in mm),
Figure 1. Samples preparation for tests: Number of samples (in brackets), samples dimensions (in
and preparation operations and tests to be carried out.
mm), and preparation operations and tests to be carried out.
These samples were cold rolled to obtain five different thickness batches: 12 samples of 1.5 mm
thick, Micrographs
2.2.2. and
12 samples of Hardness
1.25 Tests
mm thick, 12 samples of 1 mm thick, 12 samples of 0.75 mm thick and
Appl. Sci. 2019, 9, 3265 4 of 12

12 samples of 0.65
Appl. Sci. 2019,mm thick.
9, x FOR PEERThe samples thickness of each batch is expressed as “e” in Figure 1. Those 4 of 13
REVIEW
values correspond to cold work percentages of 0%, 17%, 33%, 50% and 57%, respectively.
Subsequently,
Two samples the samples selected
from each forwere
batch corrosion testsfor
selected were cut to 40 mm
micrographic in length,
tests (Figureleaving
1). Onewelds
to obtain a
approximately in the center
surface micrograph and(Figure 1). for a transversal micrograph. The surface micrographs allowed the
the other
study of the changes that take place at the surface and that could lead to a deterioration of the
2.2.2. Micrographs and Hardness Tests
protective passive layer on the stainless plate. The transversal micrographs provide information
about
Two the welding
samples from eachmicrostructure
batch were and howfor
selected themicrographic
grains are deformed by the
tests (Figure 1). rolling
One to process,
obtain a as the
surfacechanges
micrographin theandmicrostructure
the other for driven by plastic
a transversal deformationThe
micrograph. could affectmicrographs
surface the corrosion resistance of
allowed
the joints.
the study of the changes that take place at the surface and that could lead to a deterioration of the
For thelayer
protective passive micrographs, the samples
on the stainless were
plate. The cut as indicated
transversal in Figure
micrographs 2. After
provide cutting,about
information they were
polished
the welding in two stages:
microstructure andFirst
howathegrinding
grains with 200 and by
are deformed 500the
grain sizeprocess,
rolling abrasiveaspaper, followed
the changes in by a
the microstructure driven by plastic deformation could affect the corrosion resistance of the joints. a 10%
final polishing with 3 μm and 1 μm diamond paste. Finally, the samples were electroetched in
oxalic
For the acid solution. the samples were cut as indicated in Figure 2. After cutting, they were
micrographs,
polished inThetwosamestages:samples were used
First a grinding to measure
with 200 and 500the grain
hardness
size at the weld
abrasive bead,
paper, the HAZ
followed by and the base
a final
metal.
polishing with 3 µm and 1 µm diamond paste. Finally, the samples were electroetched in a 10% oxalic
acid solution.

(Rolling direction)

(a) First cut in test sample

(b) Second cut in test sample

1 Welded zone
2 HAZ (c) Transversal section after second cut
3 Base material
1 3
2

Figure 2. Samples preparation for micrographs and hardness measurement. The dashed triple line
Figure
represents the 2. Samples
rolling preparation for micrographs and hardness measurement. The dashed triple line
direction.
represents the rolling direction.
The same samples were used to measure the hardness at the weld bead, the HAZ and the
base metal.The micrographs were made with an Optikam camera (Optika, Ponteranica, Italy) software in a
The micrographs
NIKON were made
metallographic with an Optikam
microscope camera
Microphot-FX (Optika,
(Nikon, Ponteranica,
Tokio, Japan). ForItaly) software in testing,
microhardness a
NIKON metallographic microscope Microphot-FX (Nikon, Tokio, Japan). For microhardness
a Vickers micro-durometer INNOVATEST 400A (Innovatest, Townley, The Netherlands) with 300 g testing,
a Vickers
loadmicro-durometer
was used and 12INNOVATEST
s of dwell time.400A (Innovatest, Townley, The Netherlands) with 300 g
load was used and 12 s of dwell time.
2.2.3. Tensile Tests
2.2.3. Tensile Tests
Ultimate and yield strengths were evaluated by tensile tests performed on five samples from
Ultimate and(Figure
each batch yield strengths
1) usingwere
a 100evaluated by tensile
kN universal tests performed
test machine on five
Electrotest MD-2 samples fromDaganzo
(Ibertest, each de
batch (Figure 1) using a 100 kN universal test
Arriba, Spain), at a test speed of 10 mm/min.machine Electrotest MD-2 (Ibertest, Daganzo de Arriba,
Spain), at a test speed of 10 mm/min.
2.2.4. Corrosion Tests
2.2.4. Corrosion Tests
Five samples from each batch were selected for corrosion tests (Figure 1). These tests, in
Five samples from each batch were selected for corrosion tests (Figure 1). These tests, in accordance
accordance with ASTM G48-92 [31], consisted in submerging the samples during 72 h in a 10% mass
with ASTM G48-92 [31], consisted in submerging the samples during 72 h in a 10% mass (0.387 M)
(0.387 M) solution of iron(III) chloride hexahydrate (FeCl3·6H2O) electrolyte and the subsequent
solution of iron(III)
evaluation chloride
of the hexahydrate
pitting corrosion in(FeCl 3 ·6H2and
the weld O) electrolyte
HAZ zones. and
Thethe subsequent
FeCl evaluation of
3 provide the Cl− ions needed
the pitting corrosion in the weld and HAZ zones. The FeCl provide the Cl − ions needed to accelerate
3
to accelerate the corrosion rate as described in the introduction.
the corrosion rate as described in the introduction.
3. Results

3.1. Micrographs and Hardnesses

Appl. Sci. 2019, 9, 3265 5 of 12

Appl. Sci. 2019, 9, x FOR PEER REVIEW 5 of 13

3. Results
Appl. Sci. 2019, 9, x FOR PEER REVIEW 5 of 13
Appl. Figures 3–7
Sci. 2019, 9, show
x FOR PEER the transversal micrographs performed at the fusion line of welded zones
REVIEW 5 of at
13
3.1. Micrographs and Hardnesses
samples of 1.5 mm to 0.65 mm thick.
Figures
Figures 3–7 show the transversal micrographs performed atat the fusion line of welded zones atat
In these3–7
Figures 3–7show
showthe
micrographs thetransversal
transversal
the granular micrographs
deformationperformed
micrographs performed
due to rolling atthe
the
canfusion
fusion
be seenline atof
line ofwelded
bothwelded zones
zones
the weld bead at
samples
samples
samples of
of
of 1.5
1.5
1.5 mm
mmmm toto
to 0.65
0.65
0.65mmmm
mm thick.
thick.
thick.
and the HAZ. As the deformation occurred in a cold forming process, the structures changed from
InIn these
Inthese micrographs the granular deformation due toto rolling can be seen atat both the weld bead
dendritic at micrographs
these micrographs
the weld bead the togranular
the granular
equiaxialdeformation
deformation
at the HAZs due
due
and torolling
rolling
the base can
canbe beseen
metal. seen
Those atboth
both the
theweld
structuresweldbead
bead
become
and
and
and the
thethe HAZ.
HAZ.
HAZ. As
AsAs the
thethe deformation
deformation
deformation occurred
occurred
occurred inina
in a
a cold
cold
cold forming
forming
forming process,
process,
process, the
the
the structures
structures
structures changed
changed
changed from
from
from
clearly elongated as the thickness reduction increases. This difference is progressively reduced as the
dendritic
dendriticatat
dendritic the
atthe weld
weld bead
bead toto equiaxial
equiaxialatat
toequiaxial the
atthe HAZs
theHAZs and
and the base metal. Those structures become
deformation the weld
degree by bead
rolling increases, as can HAZs
be seen inthe
and thebase
Figuresbase metal.
metal.Those
3–7. Thosestructures
structuresbecome
become
clearly
clearly elongated
clearlyelongated as
elongatedasasthe the thickness
thethickness reduction
thicknessreduction increases.
reductionincreases. This
increases.This difference
Thisdifference is progressively
differenceisisprogressively reduced
progressivelyreduced as
reducedas the
asthethe
deformation
deformation
deformationdegree degree by rolling
degreebybyrolling increases,
rollingincreases, as
increases,asas can
cancan be
bebe seen
seen in
inin
seen Figures
Figures
Figures 3–7.
3–7.
3–7.

Figure 3. Transversal micrography of the non-rolled sample (1.5 mm thick) at the weld bead
(right)/heat affected zone (HAZ) (left) interface.
Figure
Figure3.3. Transversal micrography of the
the non-rolled
samplesample
(1.5 mm(1.5 mm thick)
weldat the weld
Figure Transversal
3. micrography
Transversal of the
micrography ofnon-rolled
non-rolled sample thick)
(1.5 mmat the
thick) bead
at weld bead
the(right)/heat
bead
(right)/heat
affected affected
zone affected zone
(HAZ) (left) (HAZ) (left) interface.
(right)/heat zoneinterface.
(HAZ) (left) interface.

Figure 4. Transversal micrography at the weld bead (right)/HAZ (left) interface after 17% cold
rolling.
Figure 4. Transversal
Figure micrography at theatweld bead (right)/HAZ (left) interface after 17% cold rolling.
Figure4.4.Transversal
Transversalmicrography
micrography atthetheweld
weldbead
bead(right)/HAZ
(right)/HAZ(left)
(left)interface
interfaceafter
after17%
17%cold
cold
rolling.
rolling.

Figure 5. Transversal
Figure micrography
5. Transversal at theatweld
micrography bead bead
the weld (right)/HAZ (left) (left)
(right)/HAZ interface after 33%
interface aftercold
33%rolling.
cold
rolling.
Figure
Figure5.5.Transversal
Transversalmicrography
micrographyat atthe
theweld
weldbead
bead(right)/HAZ
(right)/HAZ(left)
(left)interface
interfaceafter
after33%
33%cold
cold
rolling.
rolling.
 Appl.
Appl. Sci. Sci. 2019,
2019, 9, x FOR PEER REVIEW
9, 3265 6 of 136 of 12
Appl. Sci. 2019, 9, x FOR PEER REVIEW 6 of 13

Figure 6. Transversal micrography at the weld bead (right)/HAZ (left) interface after 50% cold
Transversal
Figure 6.Figure micrography
6. Transversal at theatweld
micrography rolling.
bead
the weld (right)/HAZ
bead (left)
(right)/HAZ interface
(left) interfaceafter
after50%
50% cold
cold rolling.
rolling.

Figure 7.Figure 7. Transversal

Transversal micrography
micrography at theatweld
the weld
beadbead (right)/HAZ
(right)/HAZ (left)
(left) interfaceafter
interface after57%
57% cold
cold rolling.
rolling.
Figure 7. Transversal micrography at the weld bead (right)/HAZ (left) interface after 57% cold
Figure rolling.
8 shows the presence of deformation induced martensite at the samples after deformation.
AlthoughFigure 8 were
the tests showscarried
the presence of deformation
out at room temperatureinduced martensite
and martensite at the issamples
formation favoredafter
by lower
Figure 8Although
deformation. shows the presence
the tests were of deformation
carried induced
out at room martensite
temperature at the samples
and martensite after
formation is
temperatures, the cold work level is high enough to compensate for the higher temperatures of the
deformation.
favored Although
by lower the tests were
temperatures, carried
the cold work out at room
level temperature
is high enough toand martensite
compensate forformation is
the higher
rolling. As stated by [32],
favored by lower
the presence of this martensite has enough
a great influence on the performance of
temperatures of thetemperatures, the cold
rolling. As stated work
by [32], thelevel is high
presence to compensate
of this martensite forinfluence
has a great the higher
on
the protective layer
temperatures
the performance that
of the covers
rolling.
of the the deformed
As stated
protective bythat
layer samples.
[32],covers
the presence of this samples.
the deformed martensite has a great influence on
Appl. Sci. 2019, 9, x FOR PEER REVIEW 7 of 13
the performance of the protective layer that covers the deformed samples.

Figure
Figure 8. Deformation
8. Deformation twinsininone
twins oneofofthe
the33%
33% cold
cold rolled
rolled samples.
samples.Martensite
Martensitegrows along
grows the the
along
deformation twin boundaries.
deformation twin boundaries.

The high levels of cold work also generated small cracks at the surface of the welded samples
(Figure 9). This leads to a decrease in the performance of the protective layer as its continuity is
broken and a slight reduction of the mechanical properties when compared to a sample with no
cracks.
 Figure 8. Deformation twins in one of the 33% cold rolled samples. Martensite grows along the
Appl. Sci. 2019, 9, 3265 7 of 12
deformation twin boundaries.

The high levels of cold work also generated small cracks at the surface of the welded samples
(Figure 9).
(Figure 9). This
Thisleads
leadstotoa decrease
a decrease in the
in the performance
performance ofprotective
of the the protective layer
layer as as its continuity
its continuity is
is broken
broken and a slight reduction of the mechanical properties when compared to a
and a slight reduction of the mechanical properties when compared to a sample with no cracks. sample with no
cracks.

Figure
Figure 9. Cracks at
9. Cracks at the
the surface
surface after
after 50%
50% cold
cold rolling.
rolling.

The results of hardness tests are shown in Table 2, in which the figures given are the average
values obtained from the five samples of each batch with their standard deviations. As can be seen,
a 50% cold work doubles the hardness of the steel, both in the joint and the base metal, which have
similar hardness values in all cases.

Table 2. Hardness test results in the welded, heat affected and base material zones.

Welded Zone HAZ Base Material

Cold Work
(HV) (HV) (HV)
0% 220 ± 5 221 ± 5 217 ± 2.5
17% 304 ± 1.5 340 ± 2 291 ± 3.7
33% 379 ± 16 435 ± 12 387 ± 7
50% 421 ± 3 470 ± 5.7 416 ± 14
57% 480 ± 3 489 ± 4.5 463 ± 1.3

3.2. Tensile Tests

The results of the tensile tests can be seen in Table 3, in which the values for the yield strength and
the tensile strength are the average values obtained from the five samples of each batch, with their
standard deviations.
3.2. Tensile Tests
The results of the tensile tests can be seen in Table 3, in which the values for the yield strength
and the tensile strength are the average values obtained from the five samples of each batch, with
Appl. Sci. 2019, 9, 3265 8 of 12
their standard deviations.

Table 3. Resistance characteristics obtained

Table 3. obtained from
from tensile
tensile tests.
tests.

ColdCold
WorkWork Tensile
TensileStrength (MPa)
Strength (MPa) Yield Strength (MPa)
Yield Strength (MPa)
0% 0% 480
480 ±
± 17
17 180 ± 180
14 ± 14
17% 17% 760 ± 20
760 ± 20 16 ± 16
360 ± 360
33% 800 ± 16 580 ± 15
33% 800 ± 16 580 ± 15
50% 1170 ± 25 930 ± 20
57% 50% 1170
1200 ±± 25
29 930 ±1120
20 ± 26
57% 1200 ± 29 1120 ± 26
3.3. Corrosion Tests
3.3. Corrosion Tests
Figure 10 shows an example of the pitting corrosion tests on a cold rolled sample.
Figure 10 shows an example of the pitting corrosion tests on a cold rolled sample.

Figure 10. Pitting at the welding and HAZ zones of a 33% cold work sample.
Figure 10. Pitting at the welding and HAZ zones of a 33% cold work sample.

Table 4 gives the average value of the yield strength and the average number of pits. The number
Table 4 gives the average value of the yield strength and the average number of pits. The number
of pits was determined in a 20 mm long area of the HAZ (whose limits are equidistant to the weld)
of pits was determined in a 20 mm long area of the HAZ (whose limits are equidistant to the weld)
using a 50× magnifying glass and the image counting system provided by the software ImageJ.
using a 50× magnifying glass and the image counting system provided by the software ImageJ.
Table 4. Yield strength and number of pits per m2 .
Table 4. Yield strength and number of pits per m2.
Cold Work Yield Strength (MPa) Pits Number (103 /m2 )
Pits Number∇
0%Cold Work Yield
180 Strength (MPa) 175
(103/m2)
17% 360 185
33% 580 225
50% 930 320
57% 1120 400

Except for the undeformed samples, all of them presented big pits that perforated the samples.

4. Analysis of Results and Discussion

Figure 11 shows the correlation between the cold work level (percentage of width reduction) and
the number of pits (an indicator of the corrosion degree). The following expression, obtained by a least
squares fit, models this correlation:

y = 165316 + 8343·e0.0585·x ,

where:

y = Pits number/m2
x = Cold work (%)
 y = Pits number/m2
x = Cold work (%)
According to [21], the linear dependence of the pit generation rate on the potential suggests that
the pitting process is controlled by an electromechanical breakdown of the passive film. This
conclusion
Appl. Sci. 2019,could
9, 3265 support the correlation found between the cold work level and the number of pits
9 of 12
at the present study, that has been represented in Figure 11.

500
450
400
Number of pits (x103/m2)

350
300
250
200
150
100
50
0
0 10 20 30 40 50 60
Cold work (%)

Figure 11.
Figure 11. Graphical
Graphical representation
representation of
of the
the correlation
correlation between
between the
the cold
cold work
work and
and number
number of
of pits
pits in
in aa
10%mass
10% masssolution
solutionof
ofFeCl ·6H22O.
FeCl33·6H

According to [21],
About the result of the
the linear dependence
corrosion of the
test, we must pitconsider
first generation
that rate on the potential
the effectiveness suggests
of the surface
that
layerthe pitting process
of chromium oxide,is which
controlled byaan
acts as electromechanical
protective agent againstbreakdown
corrosionofinthe passive
stainless film.can
steels, Thisbe
conclusion
reduced due could support
to the rollingthe correlation
mechanical found
effects between
that the cold
could lead to a work levelreduction
thickness and the number of pits at
and/or breakage
the present
of this study, that
protective hasas
layer, been represented
evidenced in Figure
by the 11. of small surface cracks in the cold rolled
presence
About the result of the corrosion test, we must first consider that the effectiveness of the surface
layer of chromium oxide, which acts as a protective agent against corrosion in stainless steels, can be
reduced due to the rolling mechanical effects that could lead to a thickness reduction and/or breakage
of this protective layer, as evidenced by the presence of small surface cracks in the cold rolled samples.
Furthermore, the study carried out in [33] focused on the welding of 304 L austenitic stainless steel
by the shielded metal arc welding process using a standard 308 L electrode, shows that, during
sensitization, chromium in the matrix precipitates out as carbides and intermetallic compounds on
grain boundary, decreasing the corrosion resistance. Similar results are found in [34], and [35] which
associates the precipitation of chromium nitride with the reduction of the corrosion resistance of the
nitrided layer.
In the AISI 304 stainless steel welding, pitting is concentrated in Cr-depleted regions adjacent to
the carbide precipitates [11]. The studies about the effect of microstructural changes in the AISI 304
stainless steel induced by TIG welding, and surely other welding techniques, on the pitting corrosion
behavior conclude that the process made the weld metal and HAZ zone more sensitive to the pitting
corrosion than the base metal [36]. This work also concludes that high heat-input (and low cooling
rate) was likely to induce the segregation of alloying elements and formation of Cr-depleted zones,
resulting in decreasing the corrosion resistance [36]. Even more, under [11] study, TIG-welds exhibit
lower pitting corrosion resistance than friction and electron beam welds. In fact, austenitic stainless
steels are prone to sensitization when subjected to higher temperatures during the manufacturing
process. In particular, the study of [27] emphasizes the essential role of temperature-affected variations
of the properties of oxide films and their effect on the pitting corrosion in the AISI 304 stainless steel.
Appl. Sci. 2019, 9, 3265 10 of 12

The pitting corrosion occurs as a result of a breakdown of the protective passive film on the metal
surface [22,37–39] and according to [25], the lowest pitting corrosion resistance behavior is shown in
the heat affected zone.
A relevant experimental result, described by [40], is the appearance of the strain-induced martensite,
transformed from austenite during the cold working process that can be observed in Figure 4. Which
could be related with the appearance of corrosion points, since the formation of micro-pitting occurs
preferentially in areas where the tensile residual stresses are the highest [41].
After analyzing the reduction of the anti-corrosion protection in AISI 304 rolled stainless steel
welding, it is worth considering how to mitigate the factors that trigger it (chromium concentration
decreases in the protective layer and deformation stresses in the material). We have previously
commented that the use of a low-carbon filler material reduces chromium carbide formation in the
grain boundaries during welding and so, maintains chromium concentration at adequate levels [6,7].
Regarding the deformation stresses reduction, heat treatments are not feasible. As a result of the
plate thicknesses considered, stress-reducing heat treatments will cause serious deformations such as
unacceptable flatness errors. Another consideration pointed out by [42] is to improve the corrosion
resistance of austenitic stainless steels, like AISI 304, through surface finishing treatments, which has
been demonstrated beneficial regarding the localized pitting corrosion properties in stainless steels [43].
However, it also must be considered that the residual stress introduced by certain surface finishes
affects the corrosion behavior of austenitic stainless steel [13].
Finally, due to the practical impossibility of avoiding the negative effects on corrosion resistance of
the manufacture of thin AISI 304 rolled stainless steel welded plates, one alternative would be to select
the thickness of the material used according to its expected use conditions, for which the information
in Table 4 could be used.

5. Conclusions
Corrosion resistance of AISI 304 rolled stainless steel welding can be altered at both the welded and
the HAZ zones due to the effects of cold rolling and the metallurgic transformations and physic-chemical
processes that occur during welding, including residual stresses distribution.
The increment of the pitting corrosion in AISI 304 rolled stainless steel welding can be attributed
to a combination of factors: The reduction of the anti-corrosion protection, the microstructural changes
resulting from the cold rolling process and the internal increased stresses.
Both the chromium concentration decrease, that causes thickness reduction and/or breakage of
the chrome oxide protective layer, and the increment of stresses in the samples have been observed
in the experimental results. Martensite induced by deformation, transformed from austenite during
rolling has also been observed in the experimental results.
All these changes, which promote the local pitting corrosion in the AISI 304 rolled stainless steel
weld, are difficult to prevent.
The pitting corrosion degree in AISI 304 cold rolled welds was evaluated in a FeCl3 solution
following the ASTM G48-11 standard. The corrosion resistance of the samples was measured using the
number of pits and correlated with the deformation level of these samples. The number of pits varied
from 175·103 pits/m2 for the undeformed samples to 400·103 pits/m2 for a 57% cold work level.
The exponential expression that correlates cold work levels and pits number, if confirmed, can be
useful in the design and material selection for products and facilities including the AISI 304 rolled
stainless steel butt-welded, since it provides a simple (not expensive) method to assess the material
thickness suitability regarding its corrosion resistance.

Author Contributions: In this investigation, F.-J.C.-C., M.P.-G. and F.S.V. conceived and designed the experiments;
F.-J.C.-C., L.S.G. and M.-A.P.-P. performed the experiments; M.P.-G., L.S.G. and F.S.V. analyzed the data; M.-A.P.-P.
contributed materials/analysis tools; M.P.-G., L.S.G. and F.S.V. wrote the paper.
Funding: This research received no external funding.
Appl. Sci. 2019, 9, 3265 11 of 12

Acknowledgments: The authors deeply thank the Universitat Politècnica de València (Spain), for the support of
this research.
Conflicts of Interest: The authors declare no conflict of interest.

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