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Influence of processing method of CoCrMo dental alloy on the corrosion

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Article in Materials and Corrosion · October 2022

DOI: 10.1002/maco.202213562

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Received: 19 September 2022 | Accepted: 8 October 2022

DOI: 10.1002/maco.202213562

ARTICLE

Influence of processing method of CoCrMo dental alloy

on the corrosion behavior in artificial saliva

Joana R. Pontes1 | Fatih Toptan1,2,3 | Ana M. P. Pinto1,4 | Edith Ariza1,5 |

Alexandra C. Alves1,2

1
CMEMS‐UMinho ‐ Center of
MicroElectroMechanical Systems, Abstract
Universidade do Minho, Azurém, Removable or fixed dental frameworks are usually made of CoCr alloys. The
Portugal
CoCr dental alloys are produced traditionally by lost‐wax casting. However,
2
IBTN/Euro – European Branch of the
Institute of Biomaterials, Tribocorrosion alternative processing routes, such as hot‐pressing, are being studied for dental
and Nanomedicine, Department of Eng. applications. The purpose of the present work was to assess the corrosion
Mecânica, Universidade do Minho,
resistance of CoCrMo dental alloy produced by conventional lost‐wax casting
Azurém, Portugal
3 and hot‐pressing. The corrosion behavior was studied in artificial saliva at
Department of Materials Science and
Engineering, Izmir Institute of 37°C by potentiodynamic polarisation tests. Immersion tests were performed
Technology, Izmir, Turkey to evaluate the growth of the passive film where electrochemical impedance
4
DEM – Department of Mechanical spectroscopy was used at different immersion periods. Results showed slightly
Engineering, Universidade do Minho,
Azurém, Portugal better corrosion resistance in terms of ipass for CoCrMo samples obtained by
5
SEMAT/UM, Universidade do Minho, hot‐pressing. On the other hand, the immersion tests showed a more stable
Azurém, Portugal and thicker passive film formed on hot‐pressed CoCrMo dental alloy, pointing
out that hot‐pressing may be considered a promising technique to produce
Correspondence
Fatih Toptan, Department of Materials CoCrMo dental structures.
Science and Engineering, Izmir Institute
of Technology, Urla 35430, Turkey. KEYWORDS
Email: fatihtoptan@iyte.edu.tr casting, CoCrMo‐dental alloys, corrosion, hot‐pressing

Funding information
Fundação para a Ciência e Tecnologia
(FCT), Grant/Award Number: UID/EEA/
04436/2019

1 | INTRODUCTION compared to noble alloys, CoCr alloys are attractive

Metallic dental restorations are placed in the oral cavity,
which is known as an extremely aggressive and complex
environment[1–6] promoting corrosion mechanisms lead-
ing to metallic ion release. Thus, allergic reactions can be
caused due to the release of corrosion products causing
the failure of the restoration.[7,8] It is well reported that
CoCr dental alloys possess excellent corrosion and wear
resistance and adequate mechanical properties.[2,5,6,9]
Considering these properties and the price of these alloys
Materials and Corrosion. 2022;1–9.
materials for frameworks of partial removable or fixed
dental prostheses.[5,10]
Traditionally, the CoCr dental restorations are
produced by lost‐wax casting (LCW) and conventional
casting methods. However, these processing routes
are known for their defects such as porosity, chemical
inhomogeneity, large grain size, and microstructures
with hard precipitates in the interdendritic zones.
Hot‐pressing (HP) is a powder metallurgy (P/M)
route, where the sintering is done under the
www.matcorr.com © 2022 Wiley‐VCH GmbH. | 1

2 |
combined action of load and temperature. Apart of
eliminating the casting defects, HP can lead to
improved mechanical and corrosion properties than
the conventional routes. [11,12]
Different processing routes might generate different
microstructures, and consequently different properties,
including corrosion behavior.[5,8,13–15] Tuna et al.[5] and
Padrós et al.[8] obtained CoCr prosthesis by CAD‐CAM
milling, casting, and laser sintering. While Tuna et al.[5]
showed that CoCr alloy produced by milling or laser
sintering presented better corrosion behavior than the
alloy obtained by the conventional casting route, Padrós
et al.[8] stated that the CoCr dental alloy produced by
CAD‐CAM milling route showed the best corrosion
behavior together with the lowest ion release. Both
studies attributed this behavior to the presence of
internal flaws. On the other hand, Doni et al.[11]
compared the corrosion and tribocorrosion behavior of
CoCrMo produced by HP to commercial CoCrMo
implant material at room and body temperatures. The
authors did not find significant differences between both
processing routes for both temperatures. However, the
wear rate of cast CoCrMo samples was three times higher
than CoCrMo obtained by HP. Henriques et al.[12]
compared the influence of the processing route (cast
and hot pressing) on microstructure, hardness, and
corrosion behavior. The authors showed that while HP
samples presented a globular microstructure, the casting
route led to a dendritic microstructure, with different
volume fractions of constituents. The differences in the
microstructure led to different corrosion behavior of the
alloys, where HP CoCrMo alloy showed improved
corrosion behavior.
Considering that the processing route can signifi-
cantly affect the electrochemical response of the alloys,
the present work aimed at comparing the corrosion
behavior of CoCrMo dental alloys obtained by conven-
tional LCW and HP.
2 | MATERIALS A ND METHODS
2.1 | Materials
Two processing routes were used to process the samples,
namely HP and LWC. Regarding HP, the humidity of
CoCrMo powder was removed by keeping them at 105°C
in a drying oven for 1 h. The samples were produced at
1000°C under vacuum (0.01 mbar), and a constant
pressure (40 MPa) with a sintering time of 30 min. The
details of the processing procedure is given else-
where.[16,17] For comparison, commercial CoCrMo
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PONTES ET AL.
TABLE 1 Chemical composition of both CoCrMo dental alloys
(wt%)
CoCrMo dental alloy Co Cr Mo Si Fe Mn Ni
Lost‐wax casted (LWC) 64.6 28.5 5.1 0.7 0.1 0.6 −
Hot‐pressed (HP) 64.6 27.7 5.7 0.6 0.2 0.8 0.1
samples produced by LCW were purchased from LabMed
Saude. The chemical compositions of both alloys,
obtained by X‐ray fluorescence spectroscopy (Phillips
X'Unique II), are given in Table 1.
Before the electrochemical tests, the samples were
metallographically prepared by grounding down to 4000
mesh SiC paper and polishing with diamond pastedown
to 1 µm. Last, the samples were ultrasonically cleaned for
10 min in propanol and 5 min in distilled water. The
samples were kept for 24 h in a desiccator to obtain
similar surface conditions.
2.2 | Electrochemical tests
Electrochemical tests consisted of open circuit poten-
tial (OCP), electrochemical impedance spectroscopy
(EIS), and potentiodynamic polarization performed in
180 ml of artificial saliva (0.4 g/l NaCl, 0.4 g/l KCl,
0.795 g/l CaCl 2 .2H2 O, 0.005 g/l Na 2 S.9H2 O, 0.69 g/l
Na 2H 2 PO4 .2H2 O, 1 g/l urea) at 37 ± 2°C by using
Reference 600 potentiostat/Galvanostat/ZRA from
Gamry Instruments. Prior to and after each test, the
pH of the artificial saliva was measured using a pH‐
meter (EUTECH Instruments pH 510) presenting a
pH value of 5.60 ± 0.05. Samples having 0.38 cm2
exposed area were placed in a conventional three‐
electrode electrochemical cell (adapted from ASTM:
G3‐89) as the working electrode where a saturated
calomel electrode (SCE) was used as the reference
electrode and a Pt electrode was used as the counter
electrode. OCP was monitored till stabilization,
and it was considered stable when ΔE < 60 mV/h.
Potentiodynamic polarization tests started at −0.25
VOCP moving in the anodic direction up to 1 VSCE at
0.5 mV/s.
EIS tests were performed at different times of
immersion (1 h, 6 h, 1 day, 2 days, and 4 days) at
corrosion potential. For each immersion time, OCP was
measured for 10 min before the EIS test. The impedance
data acquisition was done by scanning a range of
frequencies from 10 kHz to 10 mHz, with 10 points per
frequency decade, and with an amplitude of the
sinusoidal signal of 10 mV.

PONTES ET AL.
2.3 | Characterization
X‐ray diffraction with Bragg‐Brentano, Göbel mirror
mode, and CuKα radiation (Bruker D8 Discover) was
performed in both dental alloys. A scanning range (2θ) of
40°–80° was used, and the step size was set to 0.02°. The
peak identification was done using Diffrac Plus Evalua-
tion (Package Release 2006) software.
Before and after corrosion tests, the samples were
cleaned with the same procedure described previously
and the surfaces were examined by field emission gun
scanning electron microscope (FEG‐SEM, FEI Nova 200),
and the chemical composition was analyzed by EDAX
energy dispersive X‐ray spectroscopy (EDS).
3 | RESUL TS
Back‐scattered electron (BSE) SEM images together with
XRD patterns of CoCrMo alloys are shown in Figure 1.
Independently of the processing route, both CoCrMo
alloys revealed both γ and σ phases were on their XRD
patterns (Figure 1b,d). While the γ phase was identified
using ICDD 00‐001‐1259 card, the σ phase was identified
after a comparison of the present XRD results with data
F I G U R E 1 Back‐scattered electron (BSE)/scanning electron microscope (SEM) images (a, b) and X‐ray diffraction (XRD) patterns (c, d)
of as‐processed lost‐wax casted (LWC) and hot‐pressed (HP), respectively
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| 3
available for (CrCo)‐σ[10,18–22] and ICDD 00‐009‐0052.
Two different features can be observed in
Figure 1a,c between LWC and HP samples. LCW sample
presented the typical cast microstructure of CoCrMo
alloy, and it consists of γ‐Co dendritic phase formed
during the solidification process, and a secondary
σ phase. Additionally, the presence of intrinsic defects
such as porosity can be observed. HP samples presented a
two‐phase globular structure as γ matrix and a secondary
σ phase. Although both alloys presented the secondary
σ phase, this phase was presented in different volume
fractions, where it seems to be more predominant in the
case of HP.
Figure 2a presents representative potentiodynamic
polarisation curves for both CoCrMo dental alloys.
Independently of the processing route, the potentiody-
namic polarisation curves presented similar behavior
where four distinct regions can be observed. The cathodic
domain occurs for potential values below the corrosion
potential (E(i = 0)). This region is characterized by the
reduction reactions of water and of partially dissolved
oxygen. Above the corrosion potential, c.a. −0.30 VSCE,
the anodic domain is divided into three regions: until
approximately 0.05 VSCE, there was an increase of the
current density, where the anodic reactions occur leading

4 |
F I G U R E 2 Potentiodynamic polarisation curves for lost‐wax casted (LWC) and hot‐pressed (HP) samples in artificial saliva (a),
back‐scattered electron (BSE)/scanning electron microscope (SEM) surfaces images after potentiodynamic polarisation tests for LWC
(b) and HP (c) together with X‐ray spectroscopy (EDS) spectra taken from the marked zones (d, e).
to the formation of an oxide film. Between approximately
0.05 and 0.46 VSCE, the current density was constantly
leading to a well‐defined passivation plateau. Finally,
above c.a. 0.46 VSCE, there was an increase of current
density, known as transpassive region. In this region,
water oxidation and metallic oxide oxidation occur.
Figure 2b,c gives the representative BSE/SEM images
after potentiodynamic polarisation in artificial saliva
together with the respective EDS spectra for both tested
alloys. In both cases, while the γ matrix corroded
homogenously, the σ phase seems not to be affected by
corrosion.
Table 2 gives the average values of corrosion potential
(E(i = 0)), breakdown potential (Eb), and passivation
current density (ipass) values for LWC and HP samples.
The results showed no significant differences between
E(i = 0) and Eb between the tested groups. Additionally,
both samples presented similar ipass, indicating a similar
corrosion resistance.
Nyquist and Bode diagrams for different immersion
periods together with the electrical equivalent circuit
(EEC) used to fit the EIS data are shown in Figure 3. At
high frequencies (102−104 Hz), the electrolyte resistance
response can be detected where the |Z| values are
constant, and the phase angle was near 0°. The typical
capacitive behavior of a compact passive film can be
described when the phase angle present values were
approaching −80° in low and middle frequencies, which
can be observed in both CoCrMo alloys. However, the
phase angle values tended to increase as the immersion
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PONTES ET AL.
T A B L E 2 Corrosion potential (E(i = 0)), breakdown potential
(Eb), and passivation current density (ipass) values for lost‐wax
casted (LWC) and hot‐pressed (HP) samples
LWC HP
E(i = 0) (VSCE) −0.31 ± 0.03 −0.33 ± 0.02
Eb (VSCE) 0.47 ± 0.04 0.46 ± 0.03
‐2
ipass (μA. cm ) 3.31 ± 0.32 2.96 ± 0.35
period increased suggesting that the quality of the passive
film increased. As the immersion period increased, |Z| f→0
values also increased indicating that the total impedance
of the system increased. Therefore, it can be stated that
the corrosion resistance of both alloys increased as the
period of contact with the electrolyte increased. Another
approach to determine the corrosion resistance of a
system is to compare the diameters of the semi‐circles of
the Nyquist diagrams, where a better corrosion resistance
corresponds to a larger diameter. As can be observed in
both cases, the diameters of the semi‐circles increased
with the increase of the immersion period, showing that
the corrosion resistance was improved.
The proposed EEC (Figure 3e) represents the native
oxide film formed on alloy surfaces in contact with
artificial saliva and it contains an electrolyte resistance
(Re) in series with the Rox/Qox pair corresponding to the
resistance and the constant phase element (CPE) of
the native oxide film. The CPE was used to consider the
nonideal capacitance of the oxide film. Moreover,

PONTES ET AL.
F I G U R E 3 Electrochemical impedance spectroscopy (EIS) spectra in the form of Nyquist (a, b) and Bode (c, d) diagrams for different
immersion times, together with electrical equivalent circuit (EEC) used for fitting the results (e)
considering Brug's equation,[23] Equation (1) was used to
convert Qox to Cox (capacitance of the native oxide film).
 n1
Cox = Qox Re(1− n)  .
 
(1)
In impedance representation, CPE is described as
ZCPE = [Yo ( jω)n]−1 and it considers the CPE admittance
(Y0 ), the imaginary number represented by = −1 , the
angular frequency (ω), and an exponential factor
(−1 ≤ n ≤ 1). Depending on n value, the CPE may
represent a resistor (n = 0), a capacitor (n = 1), or an
inductor (n = −1). On the other hand, if n ≈ 1, it may
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| 5
represent a nonideal capacitor being influenced by the
roughness of the surface and its heterogeneities.
Figure 4 shows the evolution of OCP, Rox, Cox, and nox
through the immersion period for both alloys. After exposing
the samples to artificial saliva, the OCP for the LWC
increased while the values followed a relatively horizontal
course for HP samples. For LWC, the shift of OCP values to
nobler values as the immersion period increased is related to
the growth of the natural oxide film in contact with the
artificial saliva. On the other hand, the formation and growth
of the oxide film on HP seemed to be more stable since OCP
values remained almost constant through the immersion
period. In addition, the higher OCP values of LWC samples,

6 |
FIGURE 4 Evolution of open circuit potential (OCP) (a), Rox (b), Cox (c), and nox (d) with the immersion time in artificial saliva
suggest a less corrosion tendency, when compared with the
HP ones.
While LWC samples presented higher Rox values, HP
samples showed lower Cox values and nox values closer to
1, indicating a better quality of the passive film.
Moreover, the Cox in the case of HP samples remained
almost constant through the immersion period in
artificial saliva which may indicate that the native oxide
film formed on these samples was more stable than the
film formed on LWC samples. Also, the nox values closer
to 1 in the case of HP samples suggested a more
homogenous surface.
According to Equation (2), the capacitance of an
oxide film is inversely proportional to its thickness:
εε0 A
C= , (2)
d presence of σ‐phase may be present as individual
where ε and ε0 are the dielectric constant of the oxide
film and the vacuum permeability (8.85 × 10−14 Fcm−1),
respectively. A is the exposed area and d is the thickness
of the film. Assuming that the oxide film formed on both
alloy surfaces has the same nature, it can be stated that
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PONTES ET AL.
the oxide film formed on HP samples was always thicker
than the one formed on LWC ones.
4 | DISCUSSION
The microstructure influences considerably the mechan-
ical and corrosion resistance of metallic materials, which
is extremely dependent on the processing routes.[11,12,24]
The amount/size of porosity, chemical inhomogeneity,
large grain size and a microstructure with hard precipi-
tates in interdendritic zones are well‐known defects for
cast metals.[20] It is known that P/M routes may
significantly eliminate those casting defects. Some
studies have shown that the properties of P/M implants
are similar to those of wrought alloys.[11,12,24] The
particles or as part of a binary eutectic inside the α‐fcc
matrix.[18–21] If the volume fraction of this phase is low,
the alloy strength does not increase. On the other hand, a
high‐volume fraction of finely precipitated and inter-
granular σ‐phase leads to a significant increase in the
alloy hardness.[25,26] However, Kurosu et al.[27] stated

PONTES ET AL.
that some cracks on the CoCrMo alloy surfaces might be
caused by the brittle σ‐phase, thus it can contribute to
crevice corrosion.
Potentiodynamic polarization tests are widely used
to determine the corrosion resistance of Co‐Cr
alloys.[5,6,8,10,11,22,28–32] Although the good corrosion
resistance of the CoCr alloys is well‐reported, the
comparison of the results is difficult due to the tests
being performed in different conditions. Another impor-
tant factor affecting the corrosion behavior of these alloys
is the presence of different alloying elements and their
content. Gălăţeanu et al.[33] compared the corrosion
behavior of two commercial CoCr dental alloys. The
difference in the chemical composition of the alloys was
in the amounts of Ga and Mn. The authors showed
superior electrochemical stability for the alloy having Ga
and Mn in its composition. The alloy having Ga had the
lowest toxicity leading to a greater cell viability with a
smaller level of ROS (intracellular reactive oxygen
species), also explains the electrochemical stability. On
the other hand, Garcia‐Falcon et al.[34] studied the
corrosion behavior of CoCrMo alloys (Vitallium 2000
Plus and Vera PDI) in Ringer's solution and reported a
uniform corrosion behavior for both alloys. However, the
presence of Fe and Ni led to a lower corrosion resistance
when compared with the alloy free of those elements.
Different processing methods might lead to different
microstructures, as can be observed in Figure 1. Although
no significant differences were observed in the present work
on the corrosion response of the CoCrMo alloy, some
studies showed that the processing route might influence
the corrosion behavior of the alloy. Padrós et al.[8] compared
the corrosion and ion‐release behavior of a CoCrW dental
F I G U R E 5 Electrical equivalent circuit
(EEC) traditionally used for the fitting of
electrochemical impedance spectroscopy (EIS)
results for passive films
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| 7
alloy obtained by three different manufacturing methods
(CAD‐CAM milling, casting, and laser sintering). The
authors found that the CoCrW alloy obtained by the
CAD‐CAM milling route showed the best corrosion
behavior, presenting lower corrosion kinetics as well as
lower Co and Cr ion release. The worse corrosion behavior
of CoCrW obtained on a cast or laser‐sintered alloy was
attributed to pores, internal shrinkage or micro segregations,
typical defects from those processing routes. The presence of
these defects might lead to accelerated corrosion due to
formed micro‐galvanic cells. On the other hand, Tuna
et al.[5] used the same manufacturing methods and stated
that no statistically significant differences were observed in
the corrosion resistance between CAD‐CAM milling and
laser sintering methods. However, the casting method led to
a higher corrosion current density being significantly
different compared with the other two methods.
Figure 2a shows the corroded surfaces after potentiody-
namic polarisation tests. In both cases, a uniform dissolution
of γ matrix was observed, while the σ phase seemed not to be
affected by corrosion. Similar behavior was also observed in
the literature on alloys produced by HP or conventional
flame fusion techniques.[10,17,32] Both processing routes
showed a stable passivation plateau due to the formation
of a stable passive film. This passive film is mainly composed
of Cr2O3, however, Co and Mo oxides might have a small
contribution to the corrosion resistance of the CoCrMo
alloy.[35,36]
Several authors used EIS measurements to explore the
characteristics of the passive film. However, there is still
some controversy regarding the EEC used to fit the EIS
results of different passive films formed on CoCr alloys
(Figure 5).

8 |
Some authors[27,35,37–40] used the ECC1 (Figure 5)
containing two time constants in series, being the first
time constant described by a parallel pair (R1/CPE1)
representing the charge transfer resistance and capaci-
tance of the double layer, respectively, occurring between
the electrolyte and the outer layer. The second time
constant represents the resistance of the oxide being
described by a parallel pair (R2/CPE2). On the other hand,
the EEC2 describing also two time constants (Figure 5)
but consists of electrolyte resistance (Rs), CPE1, and CPE2,
in parallel with charge transfer resistance (R1, R2) is also
presented in the literature.[5,34,41,42] The first time constant
(R1/CPE1) is dependent on the characteristics of the
outermost film, which can be a passive film or a mixed
layer. For the low frequencies range, the (R2/CPE2) pair
describes the performance of the base metal. However,
these two time constants are overlapped making difficult
their visualisation individually. At the same time, this
behavior shows that the relaxation time constant of the
outer film is similar to the base metal. In the present work,
the passive film formed in both CoCrMo alloys in contact
with artificial saliva is described by modified Randles'
circuit (Figure 3e), consisting in an electrolyte resistance
in series with a (Rox/CPEox) pair, representing the oxide
resistance and capacitance. This EEC considers a compact
and stable passive film and is used by several authors in
the literature for CoCr alloys giving a similar electro-
chemical response.[10,16,17,43,44]
Garcia‐Falcon et al.[34] compared the corrosion
behavior evolution of two CoCrMo commercial alloys
through 1 week of immersion in Ringer's solution. EIS
results showed that, as average values, the corrosion
resistance of the alloys slightly increased over time
while the capacitance of the film slightly decreased
suggesting an increment in the thickness of the passive
film. Moreover, the n values of the CPE became closer
to 1 as the immersion period increased indicating an
increase in the homogeneity of the film. The same trend
was observed in Figure 4d, however, a more stable
passive film was noticed for HP samples. The lower nox
values and higher Cox values found for LWC samples
are possibly related to heterogeneities of the surface
type from the processing route. On the other hand, Rox
of LWC alloy was higher than HP, while Cox was higher,
even though higher values of resistance are normally
expected to lead to lower capacitance values. This
behavior might be explained by the structure of the
passive film. Milošev et al.[36] showed that although
CoCrMo alloy had the ability to passivate spontaneously
in contact with oxygen, and the passive film is mainly
composed of Cr2O3, Co and Mo oxides might also be
formed. The authors also stated that a complex layer
was formed due to the oxidation process and that both
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PONTES ET AL.
composition and thickness are dependent on potential.
A passive film, mostly composed of Cr2O3 and Cr(OH)3,
is formed at a lower potential range. On the other hand,
at higher potentials, both Co and Mo oxides became
part of the passive film. Considering the evolution of
OCP (Figure 4) for both alloys, it is possible to observe
that LWC always presented higher potential values.
Thus, it may be speculated that the incorporation of Co
and/or Mo oxides into the passive film may occur
earlier on LWC, which may explain the higher Rox
values for this alloy, whereas the passive film formed on
LWC presents more heterogeneities leading to lower nox
values.
5 | CONCLUSIONS
The influence of the processing method of CoCrMo
dental alloy on the corrosion behavior in artificial saliva
was investigated. Each processing route led to different
microstructures such as a dendritic structure on LWC
samples and a globular microstructure on HP samples.
Even though, both alloys presented a secondary σ phase
that was existing in different volume fractions. While
potentiodynamic polarisation tests showed similar corro-
sion resistance on both samples (LWC and HP),
electrochemical impedance spectroscopy revealed that
even HP samples have a slightly less corrosion resistance,
the native oxide film formed on that samples, besides
being thicker has a better quality showing a good
corrosion protection property when compared with
LWC film oxide. Therefore, within the limitations of this
study, it can be stated that HP can be considered a viable
route to produce materials with a more stable passive
film, especially considering that powder‐based processing
routes offer several advantages over the conventional
casting routes, including reduced energy consumption
and scrap formation.
AC KNOW LEDGM ENT
This study was supported by Fundação para a Ciência e
Tecnologia (FCT) with the reference project UID/EEA/
04436/2019.
C O NF L I C T O F I N T E R E S T
The authors declare no conflict of interest.
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
ORC ID
Fatih Toptan http://orcid.org/0000-0001-9138-9119

PONTES ET AL.
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How to cite this article: J. R. Pontes, F. Toptan,
A. M. P. Pinto, E. Ariza, A. C. Alves, Mater. Corros.
2022, 1–9. https://doi.org/10.1002/maco.202213562