Materials and Corrosion 2016, 67, No. 6 DOI: 10.1002/maco.

201608893 607

Influence of the surface condition on corrosion

behavior of stainless steel

€
Dedicated to Dr. Jurgen Mietz on the occasion of his 60th birthday
€rtnagl
€mpel* and A. Ho
P. Gu

The corrosion resistance of stainless steels is massively influenced by the

condition of their surface. The surface quality includes the topography of the
surface, the structure and composition of the passive layer, and the surface near
structure of the base material. These factors are influenced by final physical/
chemical surface treatments. The presented work shows significantly lower
corrosion resistance for mechanical machined specimens than for etched
specimens. It also turns out that the rougher the surface, the lower the
corrosion resistance gets. However, there is no general finding which shows if
blasted or grinded surfaces are more appropriate, but a dependency on process
parameters and the characteristics on corrosive exposure in terms of corrosion
behavior. The results show that not only the surface roughness Ra has an
influence on corrosion behavior but also the shape of peaks and valleys which
are evolved by surface treatments. Imperfections in the base material, like
sulfidic inclusions lead to a weaker passive layer, respectively, to a decrease of
the corrosion resistance. By using special passivating techniques the corrosion
resistance of stainless steels can be increased to a higher level in comparison to
common passivation.

1 Introduction pitting and/or stress corrosion cracking. The corrosion starts in

Stainless steels provide a wide range of alloys and they are
applied in various areas with a vast variety of surface treatments
such as etched, blasted, grinded, bright-annealed etc. [1].
Corrosion resistance in various environments is the most
important property of stainless steels. Surface characteristics are
important for corrosion behavior because there is an interaction
between surface and the environmental medium leading to a
passive layer. Ideally this interaction results in a clean oxide,
respectively, hydroxide surface layer. Macroscopic failures such
as pores, cracks, or a high surface roughness hinder the
generation of a contiguous passive layer on the surface.
Microscopic defects within the steel such as lattice imperfec-
tions, segregations, or inclusions may hinder the generation of a
contiguous passive layer as well as reactive behavior on the
boundary layer during the passivation process. Stainless steels,
usually applied in passivated state, show selective corrosion like
€mpel, A. H€ortnagl
P. Gu
University of Applied Sciences Constance, HTWG, Brauneggerstrasse
55, 78462 Konstanz (Germany)
E-mail: guempel@htwg-konstanz.de
areas where the only a few atoms thick passive layer is weakened
by defects such as lattice or bonding imperfections or
miscellaneous weak spots (pores, etc.). In these areas the passive
layer is degraded or even perforated. The fewer imperfections a
stainless steel contain, the purer and smoother the surface is, the
more beneficial is its corrosion behavior. Since the development
of the passive layer is occurring in an interaction between the
base material and its environment, it is possible to influence
the quality and characteristics of the passive layer by choosing
the passivating process, respectively, the passivating environ-
ment correctly. Thereby various possibilities exist for every steel
composition to influence the corrosion behavior. This on hand
work will execute a research on the system with taking a closer
look at single effects which will be confirmed by certain test
results.
2 System components, experimental work,
and discussion of influences
In Table 1 the partial components (named A to E) of the system
“stainless steel in a corrosive environment” are indicated.

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€mpel and Ho
Table 1. Division of the overall system corrosion of stainless steel into
the subsystems base material and environment
E) Environmental medium
D) Boundary layer between passive layer and environmental medium
C) Compound and structure of the passive layer
B) Boundary layer between base material and passive layer
A) Base material with defects which especially exist in the surface area as
a result of surface finishing processes
2.1 Ad A)
First of all, the base material has to provide the metallic alloying
elements to form the protective metal compound on the surface
of stainless steels, the so called passive layer. This determines
that the chromium concentration is considerably reliable for
forming a better passive layer and that the base material’s
alloying elements are significantly influencing the corrosion
resistance and the repassivation behavior. The influence of
defects in the base material on the quality and characteristics of
the protective passive layer are diversified. They vary from the
surface topography, structural defects and inclusions in the base
material to adsorbed impurities on the surface [2]. Figure 1 gives
a schematic overview of the kind of near-surface imperfections,
respectively, imperfections in the base material influencing the
passive layer development.
Caused by mechanical surface treatment the number of
lattice imperfections increases towards the surface significantly.
Figure 2 shows the characteristics in which surface imperfec-
tions in the base material increase towards the boundary layer
between base material and passive layer. Furthermore, the
Figure 1. Schematic display of lattice imperfections which can influence the development and breakdown of the passive layer in close-to-surface
areas
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Materials and Corrosion 2016, 67, No. 6
mechanical machining of the surface changes the morphology
and topography of the boundary layer between base material and
passive layer. These changes also influence the formation of the
passive layer as well as the subsequent corrosion behavior. In
addition to this effect the energy state of the surface changes
and with this further different interface phenomena may be
developed.
The influence of volumetric lattice imperfections on the
corrosion behavior was investigated intensively on example
of cold forming stainless steel sheets, these research works
have not yet led to consistent results [3]. For example it
matters if a deformation induced lattice transformation is
occurring or not. Concerning pitting corrosion resistance
one can find results showing pitting corrosion resistance
decreases with increasing cold deformation as well as results
showing higher pitting resistance with increasing level of
cold deformation.
With these lattice imperfections located closer to the
surface, the tendency of decreasing pitting resistance seems to
be a little bit more explicit. Mechanical machining of the surface
usually leads to an increased work hardening and rising rate of
lattice imperfections like dislocation density. Using a chemical
or electrochemical surface treatment a contrarily effect takes
place. Areas of lattice imperfections are removed preferentially
and therefore imperfections and discontinuities are reduced.
However, the use of chemical and/or electrochemical surface
cleaning can also result in problems. The etching process may
lead to crevices due to preferred grain boundary dissolution.
As an established result chemical or electrochemical treated
surfaces usually show an increased corrosion resistance
compared to a lower resistance at mechanical polished surfaces.
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Materials and Corrosion 2016, 67, No. 6
Figure 2. Cross-sectional diagram of stainless steels
An additional rarely considered influence is the interfacial
chemistry. In the interface of an atomic or ionic bond the atoms
or ions are in an incomplete and with it less stable bonding state
in comparison to the inside arranged atoms. The atoms at
the interface lack their binding partner whereas the atoms in
the interior are “perfect” bonded. This unfavorable bonding
state of interface atoms and their pursuit of bonding with other
atoms lead to a variety of surface and interface effects which
consequently determine the interfacial chemistry in a system.
On a clean metal surface, the very reactive surface atoms aim for
adsorption of environmental gas or water molecules due to their
imperfect setting. Additional molecules are attached (physio
sorption). The surface tension which occurs at the interface
liquid/gas or at small crevices at the interface solid/liquid
shows a capillary effect which reflects the bonding activities of
interfacial atoms and influences besides the surface topography
the passivation and corrosion behavior of stainless steels.
The influence of the various surface treatments on the
corrosion behavior will be displayed in the following findings.
Tests were carried out on common stainless steels to determine
the influence of different surface conditions on the corrosion
behavior.
2.1.1 Experimental investigations and results
The influence of the processes etching, grinding with 60 and
120 grit and glass bead blasting has been analyzed for different
Figure 3. Critical pitting potential versus modified PREN in dependence of the applied surface treatments (potential vs. SHE)
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Influence of the surface condition 609
stainless steels from a corrosion resistance point of view. To
determine the effects of the surface treatments accurately the
specimens have been prepared differently. First the specimens
were exposed in an oven at 600 8C to receive a homogeneous
heat tint layer covering the whole surface. This is to simulate
annealing colors developing during welding. These heat tints
often are the reason for final mechanical cleaning of the
surface. The influence of segregations generated by welding
in areas of fused material has been eliminated by this
approach. The achieved results depend exclusively on the
material and the applied surface procedures. The surfaces of
the second-line specimens have been melted by the TIG
procedure without using any additional weld metal. The
inserted energy was about 3 kJ/cm. Subsequently the speci-
mens were either etched, grinded, or blasted. Finally different
standardized measurements have been executed to determine
the corrosion resistance.
2.1.2 Results of current density-potential measurements
As a test medium a 3% NaCl solution was used. The current-
density-potential-curves were determined at ambient tempera-
ture with a polarization speed of 100 mV/h using a set starting
point of
200 mV. The evaluation shows the potential at which
the particular specimen reaches a total value of 1 A/m2. These
critical pitting potential values at which pitting starts are
displayed in Fig. 3 where the critical pitting potential is plotted
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610 Gu €rtnagl
€mpel and Ho
versus the calculated pitting resistance equivalent number
(PREN).
The critical pitting potential increases with raising PREN
values. The influences of applied surface treatments are brought
out significantly. When linearizing the points of measurements
with the same surface treatment, it traces that these lines are
solely shifted parallel. The lines of the etched specimens are
significantly shifted towards the increased pitting potential
compared to the grinded or blasted specimens. A significantly
increased corrosion resistance of etched surfaces compared to
mechanical machined surfaces is visible (Fig. 3). Furthermore, it
is striking that the surface treatment of common austenite, such
as 1.4301 (AISI 304), 1.4401 (AISI 316), and 1.4539 (AISI 904L) as
well as of duplex steel like 1.4462 (AISI 318LN), has a stronger
influence on the corrosion behavior compared to high-grade
materials such as 1.4565 (X2CrNiMnMoNbN25-18-5-4) and
2.4856 (NiCr22Mo9Nb).
Especially for common austenitic stainless steels it is
practically relevant to implement an increase in corrosion
resistance through the application related use of surface
treatments. Furthermore, corrosion resistance of imperfect
areas, such as heat tints, can be restored to values close to those
of the base material.
2.1.3 Results of critical pitting temperature measurements
The FeCl3-test according to ASTM G48 [4] represents another
possibility to determine the pitting resistance. The specimens
are exposed in 10% respectively 5% FeCl3-Solution. In a 24 h
cycle the temperature is increased by 5 8C. The specimens
are examined for pitting corrosion attack in each case before the
temperature rises. The test ends, as soon as pitting attack on the
test surface becomes visible. The testing solution was changed
daily. The ratio test solution/specimen surface was 10 ml/cm2. It
was differentiated between the pitting on the cutting edges and
the rolled surfaces. For evaluation only the values of the rolled
surface were considered. At this point it is to mention that the
pitting temperatures of the cutting edges are slightly shifted
towards lower values compared to the rolled surfaces [1,6]. It is
Figure 4. Critical pitting temperature versus the modified PREN in dependency of the applied surface treatment of welded and surface treated
specimens
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Materials and Corrosion 2016, 67, No. 6
practically relevant to avoid cutting edges in areas of critical
corrosion load within the construction.
In this test it becomes generally apparent that etching
leads to a partly increased pitting temperature compared to
the other examined surface treatments (Figs. 4 and 5). The
differences between the various mechanical machined surface
treatments were minor and for that reason they were not
explicitly categorized correctly. Altogether it is important to note
that for high-grade alloys in these tests the different surface
treatments do not impact the results as much as it does with
common austenitic stainless steels.
For specimens with a welding seam (Fig. 4) just as for
specimens which are completely oxidized (Fig. 5) a significantly
higher pitting temperature of etched specimens is determined.
By comparing the CPT-values of completely oxidized specimens
and the welded specimens it turns out that the pitting
temperatures differ by up to 20 8C. This influence is caused
by segregations in the weld, because the welding was done
without filler material. The nickel-base alloy 2.4856 (NiCr22-
Mo9Nb) does not show any corrosion attack until the highest
examined pitting temperature.
2.1.4 Results of spray test according to DIN 50021
The salt spray test represents a long term test. Within this
test specimens have been sprayed with a 5% NaCl-solution.
The temperature has been constant at 32 8C. The corrosion
attack at common austenitic stainless steels is visible in this
test. An exemplary display of the corrosion progress with
increasing testing time is shown in Fig. 6. The grinded
specimens started to corrode after a few hours of testing,
whereas blasted specimen showed traces of corrosion after
some days. It was obvious that the corrosion initiated at
brush marks of grinded specimens and that specimens which
were grinded with a rough grit (60) started to corrode earlier
than smoother grinded specimens grinded with 120 grit.
It explicitly demonstrates that the corrosion rate at this kind
of testing conditions correlates directly with the surface
roughness.
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Materials and Corrosion 2016, 67, No. 6
Figure 5. Critical pitting temperature (CPT) versus the modified PREN in dependency of the applied surface treatment of oxidized and surface
treated specimen
Remarkably the etched specimens exhibit an above average
corrosion resistance compared to mechanical machined speci-
mens. The mechanical machined specimens partly show
corrosion after a very short time. Furthermore, this investigation
enabled a differentiation of diverse mechanical machined
surface treatment processes. With using glass bead blasting on
specimens a constant increase in endurance was determined
compared to grinded specimens. For specimen with a welding
seam it was generally determined that especially blasted
specimen in heat affected zones showed a linear corrosion
attack. This might be due to the low thickness of the heat tint
layer in areas of close to the heat affected zones.
2.1.5 Further investigations concerning the parameters of
mechanical surface machining
The quality of the created surface but also the processing
parameters play a big role in regards of corrosion resistance. For
investigating the corrosion resistance of stainless steels a several
days lasting conditioning should be done in advance to get
comparable stability and thickness of the passive layer. Several
studies confirm a relation between an increase of the corrosion
Figure 6. Evaluation of the corrosion rate in the salt spray test versus testing time
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Influence of the surface condition 611
resistance and the exposure time between machining and testing
the specimen. During this time saturation is achieved depending
of the environment, passivation method, and base material.
According to Olsson such saturation is, e.g., produced for the
base material 1.4404 after 3 days of exposure at air with room
temperature [7]. For those reasons the surface characteristics and
quality of austenitic stainless steels may not be separated at
experimental level from the surface manufacturing process since
this is especially influencing the close-to-surface areas of the base
material of especially metastable austenitic stainless steels.
The following examination shows the influence of the
blasting medium as well as the influence of locally induced
kinetic energy through the blasting medium. Therefore, steel
panels of the base material 1.4301 (AISI 304) with a thickness of
2.5 mm are blasted with glass beads and beads made of stainless
steel. Half of the steel panels were covered with oil dispersion
immediately before blasting them. To determine the corrosion
resistance current density-potential measurements of the critical
pitting potential in the style of ASTM G61 [18] were conducted.
To characterize the surface the roughness and SEM-scans
were evaluated (compare Fig. 7).
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Figure 7. SEM pictures – shoot peening – 1st line: shot peening with stainless steel balls, 2nd line: shot peening with glass balls; 1st column: oiled
surface before surface treatment, 2nd column: surface treatment without oilfilm

It clearly illustrates that the surfaces, which were blasted
with glass beads, show a different surface topography than those
which were blasted with stainless steel beads. At the same time
the gained roughness of the surface using the example of
the value Ra is only increased slightly. The determined pitting
potential in Fig. 8 shows a higher corrosion resistance for glass
bead blasted specimens. Furthermore, the influence of the oil
dispersion film on the surface leads to an improvement in
corrosion resistance for both, glass bead, and stainless steel bead
blasted surfaces. To identify the impact of the surface processing
on the base material, the a’-martensite content is determined by
magnetic inductive measurements. Since this method of
measurement has a very limited spatial resolution the quantified
values represent an average value set through the whole cross
section.
One more surface finish, which is very important in the area
of stainless steels, is the mechanical grinding. The following
examination shows the influence of different process parameters
on the achievable surface quality and especially on the resulting
corrosion resistance. To illustrate the effect of deformation
martensite on the following manufacturing processes, sheets
from the base material 1.4301 (AISI 304) were fabricated with
accurately defined grades of deformation. For the continuing
process, sheets with an a’-martensite concentration of 0, 12, and
50% were used. As shown in Fig. 9 the martensite concentration
of the base material is saturated when the deformation is 50% or
higher.
The surface treatment is carried out with an industrial grade
surface grinding machine and two different abrasive disks
made of Al2O3-grain and SiC-grain in resin bond. To achieve the
different surface characteristics and qualities different grinding
parameters and dressed grinding disks are utilized for every
grade of deformation. The control of the grinding process is
achieved through the circumferential speed and the rate of feed.

Figure 8. Comparison of critical pitting potential, martensite content, and surface roughness for the different blasted surfaces

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Materials and Corrosion 2016, 67, No. 6
Figure 9. Mass-content of a’-martensite depending of deformation
degree for selected stainless steels [3]
As a key indicator of the corrosion behavior of the specimen
the critical pitting potential is taken into account. The
measurement is carried out with an AVESTA-cell at a testing
temperature of 35 8C. As test medium a buffered electrolyte with
a pH-value of 4.2 and 3 g/L Cl
is applied. Apart from the optical
analysis of the surface through SEM-pictures standardized
surface roughness values are determined.
As a result of the chosen grinding parameters and the used
grinding grains, different surface topographies, which influence
the corrosion resistance, have been produced. As shown in
Fig. 10 this corrosion resistance not only depends on the
achieved surface roughness Ra but also on the used grain size.
The comparison of the various martensite concentrations shows
only a slight influence on corrosion resistance. They rather affect
the corrosion behavior through the gained surface topography,
respectively, the surface roughness which was achieved. The
influence of the grain material depends on the chosen grinding
parameters. For the parameters displayed in Figs. 10 and 11 SiC-
grain leads to a significantly higher corrosion resistance. For the
parameters displayed in Fig. 12 Al2O3-grain proves to be well
suited to gain an increased corrosion resistance especially for
material with low concentrations of martensite.
Figure 10. Corrosion resistance for mechanical machined surfaces with high abrasive grinding parameters
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Influence of the surface condition 613
2.2 Ad B)
All imperfections in the base material which are situated close to
the boundary layer (B in Table 1) may as well lead to imperfection
in the passive layer. Due to this, microstructural inhomogenei-
ties such as grain boundaries, lattice imperfections, precipita-
tions, or inclusions affect the resistance of the steel. Distinctions
of chromium concentrations, for example in the surrounding of
chromium rich inclusions, solely lead to changes in the passive
layer development and weak spots appear within the passive
layer. Notably critical are inclusions of chemical instable
substances like sulfides. These inclusions are dissolved at very
low potentials. Size and shape of these inclusions are influencing
the ability to passivate the stainless steels. Fleischer et al. [5]
pointed out that already low concentrations of sulfur lead to a
higher imperfection density of the passive layer and causes
augmented pitting as shown in Fig. 13.
In order to clearly point out the influence of sulfur on the
corrosion behavior of steel, the KorroPad-test can be used. The
testing method is described by Lehmann et al. [6]. These testing
pads use potassium hexacyanoferrate (III) as indicator to
illustrate disassociated iron ions from the surface. Local effects
and defects of the passive layer appear by small spots of Prussian
blue in the KorroPad. Size and number of spots can be used to get
a conclusion of the quality and stability of the passive layer [6,8,9].
Figure 14 shows the corrosion display of two batches of steel
1.4401 (AISI 316) with 0.002% sulfur, respectively, 0.009% sulfur
for the same concentration of chloride in the testing pad.
2.3 Ad C)
The passive layer results from an interdependency between the
metal and the environment. This means that the state of the
metal surface and the environment can change the quality of the
passive layer. Since the passive layer basically consists of
chromium and oxygen the concentration of chromium in the
base material and the availability of this element at the surface
plays an important role. Although the passive layer development
starts spontaneously at a mass percentage of 12% under
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Figure 11. Corrosion resistance for mechanical machined surfaces with usual grinding parameters
atmospheric conditions, the quality of the passive layer,
respectively, the corrosion resistance of stainless steel increase
with rising chromium concentrations. The process of passivation
can be improved by the use of highly oxidizing acids, such as
nitric acid. This passivation treatment is applied at steel
manufacturers at the final product.
The dynamic behavior of the passive layer [10,11] was
discovered early. The passive layer is spontaneously developed by
reaction between metal and environment but this first layer is
changing over time influenced by the environmental conditions.
At low potentials iron exists as Fe(II) in the film and converts to
Fe(III) at the beginning of the passive area [12]. Furthermore it
seems that an influence of the potential on the concentration of
Fe in the passive layer exists, which makes the layer composition
addicted by the potential. The concentration of chromium is the
highest at the lowest potentials [13]. Also the concentration of
solved water is reduced over time and more oxidic structures will
develop [14]. Iron is displaced out of the film with an increasing
concentration of molybdenum and chromium [15].
Figure 12. Corrosion resistance for mechanical machined surfaces with low abrasive grinding parameters
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Materials and Corrosion 2016, 67, No. 6
All these effects lead to a non-ideal corrosion resistance after
the last manufacturing process, but an improvement in
corrosion resistance can be reached by resting the material in
an unpolluted moist environment. At this fact new developed
processes set their starting point. These processes use an
enhanced passivation treatment to improve the initial passive
layer significantly by shifting the iron to chromium ratio. This
leads to a high quality initial passive layer. The increased quality
of the passive layer might also develop over time in a moderate
electrolyte likewise. But in order to decrease the risk of a
corrosion attack the corresponding treatment is done immedi-
ately after the manufacturing process.
In Figs. 15 and 16 the influence of the post-treatment on
example of the Protect1 treatment [17] of the company Poligrat
GmbH is shown. In Fig. 15 is shown a depth profile of oxide
layers focused on the oxidant elements with and without
treatment. A strong increased percentage of chromium oxide
and a decreased percentage of iron oxide can be found for the
treated specimen without tempering at (a) (II). By this treatment
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Materials and Corrosion 2016, 67, No. 6
Figure 13. Influence of sulfur content on the critical pitting potential of
an austenitic stainless steel X1CrNiMoCu25-20-5 a) sulfur content
0.010%, b) sulfur content 0.003% [5]
the specimen is etched followed by a treatment with an iron
affine passivation solution which shifts the iron chromium ratio
at the surface accordingly [13].
The determined critical pitting potential was identified with
a potentiodynamic measurement according to ASTM G61 [18] at
35 8C environmental temperature. The specimens are made out
of metal sheets made of the base material 1.4301 (AISI 304) with
the surface finish 2R (cold rolled, heat treated, etched, and cold
re-rolled). To exclude the influence of the industrial etching
process, tests were carried out not only on reference specimens
(as delivered state) but also on laboratory scale etched specimens
(etched with nitric acid). Both, the industrial etched and the
laboratory scale etched specimens exhibit comparable corrosion
behavior at this level of surface quality.
Figure 14. Local corrosion at 1.4401 (AISI 316) with a) low sulfur content (0.002%/Ecrit ¼ 580 mVAg/AgCl) and b) increased sulfur content (0.009%/
Ecrit ¼ 330 mVAg/AgCl) tested with a KorroPad test [9]
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Influence of the surface condition 615
Depending on the composition of the testing electrolyte and
the surface quality, the positive effect of the passivation treatment
may be different [17,19]. There are undisputed applications
where this kind of preprocessing leads to a massive increase to
the application behavior of the parts.
Aside from the improvement of the Fe/Cr ratio, the
corrosion resistance can additionally be upgraded by an
additional heat treatment at 200 8C. Figure 16 shows that the
critical pitting potential as well as the repassivation potential may
be additionally increased by such a treatment. These electro-
chemical measurements were done in an modified electrolyte
with 3 g/L Cl
and pH-Value of 3.1 with an increased polarization
rate of 200 mV/h. If the passive layer of the base material has a
non-optimal condition or a non-optimal surface topography, this
post-treatment may lead to some additional improvements.
Figure 17 shows indicated values which belong to specimens
which were treated according to Ref. [17] and made out of the
base material 1.4509 with using a SiC abrasive paper at a 220 grit
in laboratory scale. The measurement was also executed
according to ASTM G61 [18]. Specimens with and without the
Protect1 treatment were heat treated at 200 8C. Like seen in
Fig. 16 the corrosion resistance increases depending on the final
heat treatment but the variance of the results is reduced due to
the Protect1 treatment. The heat post-treatment, without
changing the Fe/Cr ratio before, leads to a increase variance of
the pitting potential which is probably caused by an inhomoge-
neous distribution of instable Fe-oxides on the surface.
Analytical research findings show that a thermal finish at
approximately 200 8C leads to an enrichment of iron at the
surface. This supposedly represents an iron oxide layer at the
medium side of the passive layer. Figure 18 illustrates an electron
spectroscopy analysis (ESCA) of brush-finished specimens made
of 1.4301 (AISI 304) with a Protect1-finish with and without a
thermal finish treatment at 200 8C. It can be seen that the
thermal finish treatment develops an iron oxide layer with a
different intensity and location previous to the actual Cr-oxide
layer. The layer thickness of the Cr-oxide layer also increases
slightly.
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Figure 15. Depth profile of oxide layers focusing on oxidant elements with (I) untreated and (II) Protect1 treated specimens in (a) non-tempered
and (b) tempered for 10 h at 200 8C; shaded area equals bulk material (a–I, a-II [16])

To provide information about the effect of a change within
the passive layer the electrochemical impedance spectroscopy
(EIS) is used. For this, measurements are executed on specimens
like they were already used for examinations given in Fig. 16; in
delivery condition (2R), Protect1 treatment and heat finish
treatment. In interdependency with the applied equivalent
circuit diagram and the applied electrolyte a significant increase
of the contact resistance to the passive layer was monitored. The
measurements were performed in a 1 mole H2SO4 electrolyte.
The Nyquist-chart, given in Fig. 19, as well as the given indicated

Figure 16. Comparison of untreated and treated surface conditions for the critical pitting potential and the repassivation potential in dependence
on ASTM G61, material 1.4301 (AISI 304)

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Materials and Corrosion 2016, 67, No. 6
Figure 17. Comparison of different critical pitting potential according
to the surface treatment [13]
values in Fig. 20 show distinctions between treated and untreated
specimens based on a reduction of the capacity within the passive
layer with an increase of the contact resistance.
At the generation of the passive layer imperfections like
scratches on the surface, local areas with a higher grade of
deformation or grain boundaries which act as an anode whereas
the remaining passive layer represents the cathode. Under the
influence of an electrolyte, an interaction between cathode and
anode is taking place.
2.4 Ad D)
The existing boundary layer between stainless steel and
environmental medium (electrode–electrolyte interface) is
characterized by a separation of charge. Within this process an
Figure 18. ESCA from 1.4301 (AISI 304) with PROTECT1-Protection; left without tempering; right with tempering
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Influence of the surface condition 617
electrochemical double layer develops which underlies physical
principles. This is based on Helmholtz [21]. Since this process
is not only based on a rigid double layer but on additional
diffusion processes it is possible to divide this sector into
two parts: One compact layer and a layer according to Gouy-
Chapmann (diffuse double layer) [22]. The current distribution
on hand is depending on the potential difference which is given
schematically in Fig. 21. Aside from the base material and the
passive layer it is significantly influenced by the concentration
of the electrolyte [23].
2.5 Ad E)
It has to be distinguished between the medium in which the
passive layer is generated and the medium in which the passive
layer will be used. In both cases an oxidic operating component is
necessary. As explained above, the electrical conductivity of the
surrounding medium plays an important role in developing and
destructing the existing passive layer. In doing so, the passivity
of the applied base materials significantly depends on thermo-
dynamic principles [23]. To calculate the stability of a metal
the potential-pH-chart according to Pourbaix [24] is used. The
combination of pH and red/ox potential leads to a prediction
of stability (stable, actively dissolving, or to form an oxide
layer) [23,24].
3 Discussion
The mechanism of the creation of a passive layers as well as its
collapse are well investigated theoretically and practically. The
behavior on real surfaces on the contrary is not well investigated
due to various factors of influence which cannot be predicted
certainly. A large number of corrosion damage of stainless steel
show a reduction of corrosion resistance due to an unfavorable
combination of circumstances of influencing factors. Aside from
the base materials and the included inhomogeneity of the
metallic lattice the applied manufacturing technologies impact
the improvement or decline of the corrosion resistance intensely.
The findings of the critical pitting potential and critical pitting
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€mpel and Ho Materials and Corrosion 2016, 67, No. 6

Figure 19. Nyquist-Diagram of EIS measurement for AISI 304 with surface 2C–Specimen OA 25–1 and OA 25–2 without treatment; PP-20-1 and
PP20-2 with Protect1 treatment and final tempering

temperature shown above (Figs. 3–5) indicate for all tested base
materials a uniform prediction. Surfaces which are blasted with
optimized conditions exhibit an increased corrosion resistance
compared to grinded surfaces. The carried out trials with the aim
to analyze the influence of the blasting medium as well as the
grinding parameters with the base material 1.4301 (AISI 304)
shows that surface roughness less than Ra < 0.5 mm influences
the corrosion behavior significantly. Here, the influence of the
achieved surface topography and the local energy input are the
deciding factors. This is distinguished by a local increase in
deformation martensite. The absolute corrosion resistance of the
blasted specimens is caused by material delaminations which
leads to crevices on the one hand and on the other hand by a lot of
sharp peaks which cause a weakness of the passive film. It is
shown for grinded and blasted surfaces that the rougher the
surface is the more likely metastable pit growth gets [11]. For
grinded surfaces the correct selection of the grinding grain is
more important than the resulting surface roughness. The
literature mentions for non-corroding surfaces with a long life-
span in outdoor applications a recommended Ra value less than
5 mm [14]. The presented research shows that the correlation
between surface states and corrosion behavior does not only

Figure 20. Comparison of fit parameter for surface condition without and with optimized passive layer; left: capacity of double layer; right: charge
transfer resistance

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Materials and Corrosion 2016, 67, No. 6
Figure 21. Schematic representation of potential course across the passive layer and mechanism of metal solution with nonporous primary
layer [20]
depend on the Ra value. As a consequence of different abrasive
mechanisms of SiC and Al2O3 different stress states occur close
to surface areas of the part which may influence the stability of
the passive layer [25]. The influence of local imperfections on the
base material 1.4401 (AISI 316) such as manganese sulfide
inclusions were determined in this research. They stimulate a
locally stable pit growth with their dissolving [26].
By applying a selective finish treatment such as electro-
polishing the local imperfections in the passive layer can be
reduced or the iron to chromium ratio can be shifted to a higher
concentration of chromium to significantly improve the corro-
sion resistance. The influence of the chromium concentration is
evident at the critical pitting potential as well as the repassivation
potential. The mechanism of action on the repassivation
potential after the pitting on the surface shall be an inherent
part of our research. The conducted EIS-measurements show a
significant increase of the electrical resistance at the passive layer
in this context.
4 Conclusions
The presented research findings confirm the superiority of
etched respectively electropolished surfaces compared to grinded
or blasted surfaces. For grinded and blasted surface finishes it is
obvious that the selection of process parameters has a significant
influence on the corrosion resistance even for surfaces with a
roughness less than Ra < 5 mm. For grinding, a higher corrosion
resistance can be achieved by using SiC as a grain material. The
interaction of different system constraints under real conditions
has to be considered from different point of views to gain overall
evidence on corrosion behavior. With the change in the Fe/Cr
ratio to a higher chromium concentration in the passive layer, the
corrosion resistance increases considerably which may be caused
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Influence of the surface condition 619
by an increase of the electrochemical resistance of the passive
layer.
5 References
[1] P. G€umpel, Rostfreie St€ahle, Expert-Verlag, Renningen 2007.
[2] W. Bergmann, Werkstofftechnik, Carl Hanser Verlag, M€ unchen
2000.
[3] P. Seemann, Dr. -Ing. Thesis, RWTH Aachen, Germany
2014.
[4] ASTM G 48: Standard Testing Method of Pitting and Crevice
Corrosions Resistance of Stainless Steel and Related Alloys
by the use of Ferric Chloride Solution, 1980.
[5] H.-J. Fleischer, N. Arlt, P. G€umpel, R. Grundmann, Thyssen
Edelstahl Techn. Berichte 14 1988, Volume 1, 3–11.
[6] J. Lehmann, A. Burkert, J. Mietz, Mater. Corros. 2016, 67, 84.
[7] J. Olsson, Passivation Treatment of Stainless Steel, Acom – A
Corrosion Management and Applications Engineering Maga-
zine, Outokumpu Stainless AB, Avesta/Sweden 2004.
[8] A. Burkert, Detektion korrosionsempfindlicher Oberfl€achen
nichtrostender St€ahle durch die Verarbeiter, Schlussbericht zu
IGF-Vorhaben, Berlin 2014.
[9] A. Burkert, Angepasste Pr€ uf- und Untersuchungsverfahren f€ur
das Bauwesen
Teil 1: Korrosionsverhalten nichtrostender
St€ahle und Aluminium, GfKORR AK Sitzung Bauwesen,
Helgoland 2013.
[10] T. Shibata, T. Takeyama, Nature 1976, 260, 315.
[11] G. Okamoto, K. Tachibana, S. Nishiyama, T. Sugita, in:
Proceeding of the Japan-USA Symposium: Passivity and its
breakdown of iron and iron-base alloys, R. W. Staehle, H.
Okuda, pp. 106–109, 1975.
[12] S. Haupt, H. H. Streblow, Corros. Sci. 1989, 29, 163.
[13] B. K€ammerer, Dr.-Ing. Thesis, Universit€at Augsburg,
Germany 2012.
[14] J. H. Qiu, Surf. Interface Anal. 2002, 33, 830.
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

620 Gu €rtnagl
€mpel and Ho
[15] A. Rossi, B. Elsner, in: Proceeding of 12th International
Corrosion Congress, Houston, pp. 2120–2130, 1993.
[16] B. K€ammerer, S. Horn, F. Haider, G. Mori, J. Haberl, H.
Wieser, in: Proceeding of EUROCORR 2008, The European
Corrosion Congress in Edinburgh, Scotland, p. 1308. 2008.
[17] O. Boehme, S. Piesslinger-Schweiger, Verfahren zum thermo-
chemischen Passivieren von Edelstahl, Patentnr. WO2008107082
A1, 2008.
[18] ASTM G61: Standard Test Method for Conducting Cyclic
Potentiodynamic Polarization Measurements for Localized
Corrosion Susceptibility of Iron–, Nickel-, or Cobalt-Based
Alloys 2014.
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
15214176, 2016, 6, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/maco.201608893 by Rwth Aachen Hochschulbibliothe, Wiley Online Library on [17/06/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Materials and Corrosion 2016, 67, No. 6
[19] A. Leonhardt, Bachelor Thesis, Johannes Gutenberg Uni-
versit€at Mainz, Germany 2015.
[20] H. J. Engell, Stahl und Eisen 1987, 107, 1215.
[21] H. Helmholtz, Annalen der Physik und Chemie 1853, 165,
211.
[22] M. Gouy, J. Phys. Theor. Appl. 1910, 9, 457.
[23] P. Schmuki, J Solid State Electrochem. 2002, 6, 145.
[24] M. Pourbaix, Atlas d‘equilibres electrochimiques, Gautier-Vil
lars & Cie, Paris 1963.
[25] M. Duscha, Dr.-Ing. Thesis, RWTH Aachen, Germany 2014.
[26] G. Hultquist, C. Leygraf, Corr. 1980, 36, 6.
(Received: February 4, 2016) W8893
(Accepted: February 21, 2016)
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