metals
Article
The Tribo-Corrosion Behavior of Monel 400 Alloy in Marine
Environment at Varied Rotational Velocities
Yuhua Zhu 1,2 , Jianzhang Wang 1, *, Hao Liu 1 and Fengyuan Yan 1, *
Citation: Zhu, Y.; Wang, J.; Liu, H.;
Yan, F. The Tribo-Corrosion Behavior
of Monel 400 Alloy in Marine
Environment at Varied Rotational
Velocities. Metals 2022, 12, 1503.
https://doi.org/10.3390/
met12091503
Academic Editor: Thomas Fiedler
Received: 3 August 2022
Accepted: 8 September 2022
Published: 11 September 2022
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
published maps and institutional affil-
iations.
Copyright: © 2022 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Metals 2022, 12, 1503. https://doi.org/10.3390/met12091503
1 State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy
of Sciences, Lanzhou 730000, China
2 Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences,
Beijing 100049, China
* Correspondence: wangjz@licp.cas.cn (J.W.); fyyan@licp.cas.cn (F.Y.)
Abstract: Monel 400 alloy is widely employed in marine engineering equipment due to its excellent
corrosion resistance, high strength and toughness. In this paper, the tribo-corrosion behavior of
Monel 400 alloy in seawater under different rotational velocities was investigated by a pin-disk
tribometer with an integrated electrochemical cell. The results revealed that the material loss rate
and friction coefficient of the Monel 400 alloy, after tribo-corrosion and mechanical wear tests,
increased with increasing rotational velocity. Under mechanical-wear conditions, the material loss
rate increased with the sliding distance extension at higher velocities, and then more serious crack
nucleation and propagation occurred at the subsurface. Under tribo-corrosion conditions, when the
rotational velocities increased from 0.125 m/s to 0.5 m/s, the thickness of the corrosion product’s
layer was reduced from 50 nm to 30 nm; that is, the lubrication of the corrosion product became
worse. As a result, the material-loss rate and friction coefficient increased significantly at the velocity
of 0.5 m/s. Importantly, the antagonistic effect, rather than the synergistic effect, between corrosion
and mechanical wear, has been verified for the tribo-corrosion of Monel 400 alloy in seawater, and
the mechanism was analyzed.
Keywords: Monel 400 alloy; antagonistic effect; corrosion product; sliding distance; crack nucleation
1. Introduction
Recently, there has been an increasing demand for friction parts with high performance
to serve in marine engineering [1–3]. Among various metallic materials, Ni-Cu alloys are
more frequently used for marine applications due to their excellent corrosion resistance [4,5].
However, the characteristics of poor lubricity and strong corrosivity of seawater usually
lead to serious tribo-corrosion problems.
For marine equipment, the working condition parameters of different friction pairs are
different, including load, velocity and movement mode. Among them, velocity is one of the
key parameters for the normal operation of friction components, which has a great influence on
the tribological behavior of materials [6–9]. Over the past 30 years, much effort has been made
regarding the influence of rotational velocity in corrosive environments [10–13]. Generally, the
material loss of the alloy after the tribo-corrosion process is larger than the additive material
loss of mechanical wear and corrosion acting independently [14,15]. The corrosion–wear
interaction contributes a nonnegligible component to the total material loss [16,17]. Under such
conditions, the impact mechanism of rotational velocity on the tribo-corrosion behavior of alloy
is mainly divided into two aspects, including the repassivation rate for the damaged surface
and subsurface deformation [18]. The wear rate of the Ni-17.5Si-29.3Cr alloy in H2 SO4 solution
increases with the rotational velocities increasing, due to crack initiation and propagation [19].
A similar growing trend is also determined in titanium alloy in a Ringer solution, where, at the
highest rotational velocity, the material loss and synergistic factor are the highest [20].
https://www.mdpi.com/journal/metals
Metals 2022, 12, 1503 2 of 12

Among Ni-Cu alloys, Monel 400 alloy is widely employed in marine engineering
due to its excellent corrosion resistance, good strength and toughness. Our previous
studies have explored the influence of applied load and potential on its tribo-corrosion
behavior [21,22]. As a single-phased Ni-Cu alloy, Monel 400 alloy exhibits a unique
interaction between wear and corrosion. An abnormal antagonistic effect of corrosion on
mechanical wear is found, which is highly related to the lubricating performance of the
nano-spherical corrosion product which is only generated in tribo-corrosion conditions.
However, for the Monel 400 alloy, the influence mechanism of rotational velocity on tribo-
corrosion behavior and the resultant change in microstructure under the dual action of
corrosion and mechanical wear remain unclear.
In this study, the influence of rotational velocity on the tribo-corrosion behavior
of Monel 400 alloy was studied. The quantitative calculation was used to evaluate the
interaction of corrosion and mechanical wear of the Monel 400 alloy. Special attention
was focused on the formation of the corrosion product’s layer at the surface and the
microstructure evolution at the subsurface of the Monel 400 alloy.

2. Experiment
2.1. Materials
The chemical component (wt%) of Monel 400 alloy is placed in Table 1, which was
purchased from Shaanxi Qingye Special Materials Co., Ltd. (Xi’an, China). The counterpart
Al2 O3 pin was provided by Dehe Special Porcelain Factory (Zhejiang, China). The corrosion
medium is artificial seawater, prepared according to ASTM D1141-98. The pH value was
adjusted to 8.2 using 0.1 mol/L NaOH solution. The chemical compositions are listed in
Table 2.

Table 1. Chemical components of the Monel 400 alloy.

Element Cu Fe Mn Si C S P Ni
Content (wt.%) 29.65 1.85 1.09 0.22 0.08 0.003 0.003 Bal.

Table 2. The chemical compositions of seawater.

Components Concentration (g/L)

NaCl 24.53
MgCl2 5.20
Na2 SO4 4.09
CaCl2 1.16
KCl 0.695
NaHCO3 0.201
KBr 0.101
SrCl2 0.025
H3 BO3 0.027
NaF 0.003

Before wear tests, the specimens of Monel 400 alloy were machined into annular
shapes with an external diameter of 54 mm, internal diameter of 38 mm and height of
13 mm. The sliding surfaces of all specimens were polished by 800 mesh SiC sandpaper
and ultrasonically washed with ethanol. After that, the other surfaces of the specimens
were covered with insulating paint to avoid corrosion expect for the sliding surfaces. The
size of Al2 O3 counterpart was Φ 4.6 × 15 mm, and the working surface was in spherical
form with a radius of 4.75 mm.

2.2. Tribo-Corrosion Measurement

To monitor the electrochemical signal of Monel 400 alloy during sliding in situ, a
modified MMW-1 pin-on-disk wear device equipped with a PARTAT 3000A electrochemical
 2.2. Tribo-Corrosion Measurement
To monitor the electrochemical signal of Monel 400 alloy during sliding in situ, a
Metals 2022, 12, 1503 3 of 12
modified MMW-1 pin-on-disk wear device equipped with a PARTAT 3000A electrochem-
ical workstation (Ametek, Bowen, PA, USA) was used. A three-electrode system was em-
ployed to collect electrochemical signal, using a Monel 400 ring as the working electrode,
workstation
a Pt gauze as(Ametek, Bowen,
the counter PA, USA)
electrode and was used. A three-electrode
an Ag/AgCl electrode as thesystem waselectrode.
reference employed
to collect
Both electrochemical
tribo-corrosion andsignal, using a Monel
mechanical 400 ring
wear tests wereas the working
performed at 75electrode,
N for 60 amin Pt
gauze as the counter electrode and an Ag/AgCl electrode as the reference electrode.
under rotational velocities ranging from 0.125 m/s to 0.5 m/s. For tribo-corrosion tests, the
openBoth tribo-corrosion
circuit potential wasand mechanical
monitored beforewear testsfor
sliding were performed
20 min, duringatsliding
75 N forfor 60
60 min
min
under rotational velocities ranging from 0.125 m/s to 0.5 m/s. For
and after sliding for another 20 min. The mechanical wear test was conducted withtribo-corrosion tests,
an
the openpotential
applied circuit potential
of −0.9 Vwas monitored
to inhibit before sliding
electrochemical for 20 and
corrosion, min,the
during slidingwere
specimens for
60 min andinafter
immersed sliding
seawater for another
before and after20sliding
min. The mechanical
for 20 wear testThe
min, respectively. was conducted
dynamic po-
with an applied potential of − 0.9 V to inhibit electrochemical corrosion, and
larization tests were measured with a scan rate of 10 mV/s from −0.7 V to −1210.2 V under the specimens
were
staticimmersed
corrosion inandseawater before and
tribo-corrosion after
tests, sliding for 20 min, respectively. The dynamic
respectively.
polarization tests were measured with a scan rate of 10 mV/s from −0.7 V to −1210.2 V
under static corrosion and tribo-corrosion tests, respectively.
2.3. Characterization
A JEM−5600LV scanning electron microscope (SEM) (JSM-5601LV, Japan Electron
2.3. Characterization
Optics Laboratory, Akishima, Japan) was utilized to observe the morphology of the dam-
A JEM−5600LV scanning electron microscope (SEM) (JSM-5601LV, Japan Electron Op-
aged surface and subsurface of the Monel 400 alloy. X-ray photoelectron spectroscopy
tics Laboratory, Akishima, Japan) was utilized to observe the morphology of the damaged
with an Al Kα X-ray source (Thermo Scientific, Waltham, MA, USA) was employed to
surface and subsurface of the Monel 400 alloy. X-ray photoelectron spectroscopy with an
analyze the chemical composition of the corrosion product. The binding energy was cali-
Al Kα X-ray source (Thermo Scientific, Waltham, MA, USA) was employed to analyze the
brated bycomposition
chemical the C1s peakofbinding energyproduct.
the corrosion at 284.8 eV.
TheTo study energy
binding the microstructure evolution
was calibrated by the
underneath the damaged surface, a Helios G4 UX Focus Ion Beam (FIB) was used
C1s peak binding energy at 284.8 eV. To study the microstructure evolution underneath to take
the
samples from
damaged the asliding
surface, Heliossurface, and a Ion
G4 UX Focus thinBeam
membrane wasused
(FIB) was prepared,
to takewhich wasfrom
samples ob-
served
the by asurface,
sliding Tecnai and
G2S-Twin F20 transmission
a thin membrane electron which
was prepared, microscope (TEM) (FEI,
was observed by aLexing-
Tecnai
ton, KY, USA).
G2S-Twin F20 transmission electron microscope (TEM) (FEI, Lexington, KY, USA).

3. Results
3.1. Microstructure of Monel
Monel 400
400 Alloy
Alloy
The TEM morphology
morphology and selected-area electron diffraction (SAED) pattern of the the
pristine 400 alloy
pristine Monel 400 alloyare
areshown
shownininFigure
Figure1. 1. From
From Figure
Figure 1a, equiaxed
1a, the the equiaxed grains
grains (~50
(~50 nm) were
nm) were observed.
observed. FigureFigure 1b exhibits
1b exhibits regularregular two-dimensional
two-dimensional diffraction
diffraction spots,
spots, which
which are consistent
are consistent with thewith the diffraction
diffraction pattern pattern of the single-phased
of the single-phased Monel 400 Monel
alloy400 alloy
in the in
face-
the face-centered cubic (FCC) crystalline
centered cubic (FCC) crystalline structure. structure.

Figure 1.
1. (a) Bright field TEM image
image and
and (b)
(b) selected-area
selected-area electron
electron diffraction
diffraction (SAED)
(SAED) pattern of
Monel 400 alloy.
Monel 400 alloy.

3.2.
3.2. Electrochemical
Electrochemical Corrosion
Corrosion Behavior
Behavior
Figure 2a shows the open
Figure 2a shows the open circuit potential
circuit curves
potential of the
curves Monel
of the 400 alloy
Monel under
400 alloy different
under dif-
rotational velocities.
ferent rotational Before sliding,
velocities. the OCPthe
Before sliding, wasOCP
stable
was −0.23 V
at stable at because
−0.23 V of the presence
because of the
of the passive
presence film.
of the Withfilm.
passive the onset
Withof sliding,
the onset the OCP ofthe
of sliding, the OCP
Monel of400
thealloy
Moneldropped
400 alloyto
− 0.43 V at 0.125 m/s and further decreased to − 0.45 V, − 0.47 V and − 0.50
dropped to −0.43 V at 0.125 m/s and further decreased to −0.45 V, −0.47 V and −0.50 V atV at 0.25 m/s,
0.375 m/s 0.375
0.25 m/s, and 0.5 m/s,
m/s andrespectively. This result indicated
0.5 m/s, respectively. This resultthat the passive
indicated thatfilm
thewas damaged
passive film
by mechanical wear and that the damage degree increased with the rotational velocity
increasing. As the sliding proceeds, the OCP became stable with the achievement of an
equilibrium between passivation and repassivation. When sliding stopped, the OCP value
moved in the positive direction and eventually reached the initial potential of the Monel
400 alloy, indicating totally repassivation at the wear track. Figure 2b shows the Tafel
 Metals 2022, 12, x FOR PEER REVIEW 4 of

was damaged by mechanical wear and that the damage degree increased with the rota-
tional velocity increasing. As the sliding proceeds, the OCP became stable with the
Metals 2022, 12, 1503 4 of 12
achievement ofwas an damaged by mechanical
equilibrium wear and that
between passivation and therepassivation.
damage degreeWhen increased with the ro
sliding
stopped, the OCP value moved in the positive direction and eventually reached the initial with t
tional velocity increasing. As the sliding proceeds, the OCP became stable
potential of theachievement
Monel 400 alloy,of anindicating
equilibrium between
totally passivation
repassivation andwear
at the repassivation.
track. Figure When slidi
curves
2b shows with
theand stopped,
Tafelwithout the OCP
curvessliding. value
with andBefore moved in
sliding,
without the positive
the corrosion
sliding. direction and
potential
Before sliding, eventually
Ecorr of Monel
the corrosion reached
400 the init
potential
alloy was
Ecorr of potential
determined
Monel 400 alloy of
to be the
was Monel
−0.37 400
V. When to
determined alloy, indicating
sliding
be −0.37against totally repassivation
the Al2sliding
V. When O3 ceramic, at the
the the
against wear
Al2Otrack.
corrosion 3
Figu
potential 2b shows
Ecorrcorrosion
ceramic, the the Tafel
shifted topotential curves
the negative with and
Ecorr direction.
shifted to At without
the0.125 sliding. Before
m/s, direction.
negative sliding,
the corrosion the
potential
At 0.125 corrosion
m/s,was
the potent
− 0.45 V, which Eslowly
corr of Monel 400 alloy
decreased to − was
0.5 V determined
as the to bevelocity
rotational −0.37 V.increased
When slidingto 0.5against
m/s, the Al2
corrosion potential was −0.45 V, which slowly decreased to −0.5 V as the rotational veloc-
indicating
ity increasedthattoceramic,
the the corrosion potential E
0.5 electrochemical
m/s, indicating corrosion
shifted
ofcorrthe
that the electrochemicalMonel to 400
the negative
alloy was
corrosion
direction.
promoted
of the
At 0.125
Monel 400 by m/s, t
mechanical wear.corrosion potential was −0.45 V, which slowly decreased to −0.5 V as the rotational velo
alloy was promoted by mechanical wear.
ity increased to 0.5 m/s, indicating that the electrochemical corrosion of the Monel 4
alloy was promoted by mechanical wear.

Figure 2.
Figure 2. (a)
(a) Open
Open circuit
circuit potential
potential (OCP)
(OCP) curves
curves and
and (b)
(b) Tafel
Tafel curves
curves under
under different
different rotational
rotational
Figure 2. (a) Open circuit potential (OCP) curves and (b) Tafel curves under different rotatio
velocities in seawater.
velocities in seawater.
velocities in seawater.
3.3. Tribo-Corrosion
3.3. Tribo-Corrosion Behavior
Behavior
3.3. Tribo-Corrosion Behavior
Figure 33shows
Figure showsthe thetotal
total material
material lossloss
raterate
andand the friction
the friction coefficient
coefficient underunder both
both tribo-
Figure 3 shows the total material loss rate and the friction coefficient under bo
tribo-corrosion-
corrosion- and mechanical-wear
and mechanical-wear conditions conditions
at different atrotational
differentvelocities.
rotationalGenerally,
velocities. it
tribo-corrosion- and mechanical-wear conditions at different rotational velociti
Generally,
was observed it was
that observed
the total that theloss
material total material
rate and loss rate
friction and friction
coefficient under coefficient
mechanical under
wear
Generally, it was observed that the total material loss rate and friction coefficient und
mechanical
were wear
larger than wereunder
those
mechanical
larger
wear
than those under
tribo-corrosion,
were larger than
tribo-corrosion,
which
thoseincreased which
with the increased
under tribo-corrosion, rotational with
whichvelocity
the
increased with t
rotational velocity
increasing under increasing
both conditions.
rotational under both conditions.
Under tribo-corrosion
velocity increasing Under tribo-corrosion
conditions, Under
under both conditions. the total conditions,
material loss conditio
tribo-corrosion
rate and material
the total friction coefficient
loss rate andof Monel
friction 400 alloy
coefficient were
of 31.8
Monel mm/y
400 and
alloy
the total material loss rate and friction coefficient of Monel 400 alloy 0.32
were at
31.8 0.125
werem/s,
mm/y and
31.8 mm/y a
respectively.
0.32 at 0.125As the
m/s, rotational
respectively. velocity
As theincreased
rotational to 0.5 m/s,
velocity the total
increased material
to 0.5 loss
m/s,
0.32 at 0.125 m/s, respectively. As the rotational velocity increased to 0.5 m/s, the to rate
the and
total
friction
materialcoefficient
loss rate of the
and
material Monel
friction
loss rate 400
and alloy
coefficient increased
of
friction the Monel
coefficient to 120.5
400
of mm/y
thealloy
Monel andalloy
increased
400 0.43, respectively.
toincreased
120.5 mm/y to 120.5 mm
Similarly, underand mechanical-wear
and 0.43, respectively. conditions, when the rotational velocity
0.43, respectively. Similarly, under mechanical-wear conditions,rotational
Similarly, under mechanical-wear conditions, when increased
the whenfromthe rotation
0.125 m/sincreased
velocity to 0.5velocity
m/s, the
from material
0.125
increased m/s loss rate
to 0.5
from increased
m/s,
0.125 m/s the from
m/s,88.8
to material
0.5 mm/y
loss
the to loss
314.8rate
rate increased
material mm/y,
from and
88.8 from 8
increased
the
mm/y friction coefficient
to 314.8 mm/y,
mm/y to increased
and themm/y,
314.8 fromand
friction 0.35 tofriction
0.45.increased
coefficient
the from
coefficient 0.35 to from
increased 0.45. 0.35 to 0.45.

Figure 3. (a) TotalFigure 3. (a)

material Total
loss ratematerial
and (b)loss rate and
friction (b) friction
coefficient coefficient
of Monel of Monel
400 alloy 400 alloyunder
in seawater in seawater und
Figure 3. (a) Totalboth
material loss rate and
tribo-corrosion- and(b) friction coefficient
mechanical-wear of Monel 400different
conditions, alloy in seawater under
both tribo-corrosion- and mechanical-wear conditions, with different with rotational
rotational velocities velocities rangi
ranging
both tribo-corrosion-
from and
0.125mechanical-wear
m/s to 0.5 m/s. conditions, with different rotational velocities ranging
from
from 0.125
0.125 m/s to 0.5
m/s to 0.5 m/s.
m/s.

To evaluate the interaction between the corrosion and mechanical wear of the Monel
400 alloy in artificial seawater, extensive calculations were performed according to ASTM
G119-09. The corresponding results are shown in Figure 4. From Figure 4a, as the rotational
velocity increased from 0.125 m/s to 0.5 m/s, the total corrosion rate of the Monel 400 alloy
Metals 2022, 12, x FOR PEER REVIEW 5 of 12

To evaluate the interaction between the corrosion and mechanical wear of the Monel
Metals 2022, 12, 1503 5 of 12
400 alloy in artificial seawater, extensive calculations were performed according to ASTM
G119-09. The corresponding results are shown in Figure 4. From Figure 4a, as the rota-
tional velocity increased from 0.125 m/s to 0.5 m/s, the total corrosion rate of the Monel
during
400 alloy tribo-corrosion slightly increased
during tribo-corrosion from 0.35 mm/y
slightly increased from 0.35 to 0.44
mm/ymm/y, which
to 0.44 mm/y,indicates
which
accelerated electrochemical
indicates accelerated corrosion corrosion
electrochemical because ofbecause
mechanical wear. Figure
of mechanical 4b shows
wear. Figurethe 4b
influence of corrosion on mechanical wear under the tribo-corrosion
shows the influence of corrosion on mechanical wear under the tribo-corrosion condition. condition. Both
the
Bothtotal
the wear rate and
total wear ratepure mechanical
and pure wearwear
mechanical rate increased with with
rate increased the rotational velocity
the rotational ve-
increasing,
locity increasing, being 31.4 mm/y and 88.3 mm/y at 0.125 m/s and increasing tomm/y
being 31.4 mm/y and 88.3 mm/y at 0.125 m/s and increasing to 120.0 120.0
and
mm/y 314.8
andmm/y at 0.5 at
314.8 mm/y m/s,
0.5 respectively. However,
m/s, respectively. the pure
However, mechanical
the pure wearwear
mechanical rate was
rate
larger than the
was larger thantotal
thewear
total rate,
wearsuggesting that electrochemical
rate, suggesting corrosion
that electrochemical has an antagonistic
corrosion has an an-
effect on mechanical
tagonistic wear. Since
effect on mechanical the Since
wear. corrosion rate was far
the corrosion rateless
wasthan the wear
far less rate,wear
than the the
total material loss rate was determined by the wear rate W 0 , and the interaction
rate, the total material loss rate was determined by the wear rate W0, and the interaction S S between
corrosion and mechanical
between corrosion wear was
and mechanical oriented
wear by the by
was oriented degree of corrosion-inhibited
the degree wear
of corrosion-inhibited
∆W c , as shown in Figure 4c. It proves that there exists a negative synergy
wear ΔWc, as shown in Figure 4c. It proves that there exists a negative synergy between between corrosion
and mechanical
corrosion wear for the
and mechanical Monel
wear 400Monel
for the alloy, under various
400 alloy, under velocities.
various velocities.

Figure 4.
Figure 4. (a)
(a)The
Thetotal corrosion
total corrosionrate (Cw(C
rate ), pure corrosion rate (C0) and the change in corrosion caused
w ), pure corrosion rate (C0 ) and the change in corrosion
by mechanical wear (∆Cw); (b) total wear rate (Wc), mechanical wear rate (W0) and the change in
caused by mechanical wear (∆Cw ); (b) total wear rate (W c ), mechanical wear rate (W 0 ) and the
wear rate caused by corrosion (∆Wc); and (c) the contribution of wear (W0), corrosion (C0) and me-
change in wear rate caused by corrosion (∆W c ); and (c) the contribution of wear (W 0 ), corrosion (C0 )
chanical wear-corrosion interaction (S) in total material loss rate (T), at different rotational velocities
and mechanical wear-corrosion interaction (S) in total material loss rate (T), at different rotational
in seawater.
velocities in seawater.
3.4. Damage
3.4. Damage Morphologies
Morphologies
Figure 5 shows
Figure 5 shows thethe representative damaged surface
representative damaged surface of
of the
the Monel
Monel 400
400 alloy
alloy at
at different
different
rotational velocities in seawater. It was noticed that the wear of Monel
rotational velocities in seawater. It was noticed that the wear of Monel 400 alloy aggravated 400 alloy aggra-
vated under both conditions, with the rotational velocity increasing.
under both conditions, with the rotational velocity increasing. There were numerous There were numer-
ous parallel
parallel grooves
grooves together
together withpeelings
with flaky flaky peelings on the damaged
on the damaged surface
surface under under tribo-
tribo-corrosion-
corrosion-
and and mechanical-wear
mechanical-wear conditions,conditions,
which was which was
a typical a typical characteristic
characteristic of delami-
of delamination wear
nation
and wear and
became more became
prominentmoreat prominent at highervelocities.
higher rotational rotational velocities.
ComparedCompared with
with the tribo-
the tribo-corrosion condition, the flaky peeling was more serious
corrosion condition, the flaky peeling was more serious under mechanical wear at the under mechanical wear
at the rotational
same same rotational
velocity.velocity. For example,
For example, at 0.5the
at 0.5 m/s, m/s, the dimensions
dimensions of flaky
of flaky peelingpeeling
were
were 183 μm in length and 72 μm in width under tribo-corrosion
183 µm in length and 72 µm in width under tribo-corrosion conditions, which increased conditions, which in-
creased
to 205 µm to and
205 155
μm µm andunder
155 μm under independent
independent mechanical mechanical wear, respectively.
wear, respectively. The damaged The
damaged
surface surface morphology
morphology observations observations partially explained
partially explained whymaterial
why the total the total loss
material loss
rate was
rate was
higher higher
under theunder the condition
condition of mechanicalof mechanical wear, as
wear, as shown in shown
Figure in
4c.Figure 4c.
The cross-section morphologies of the Monel 400 alloy are presented in Figure 6. At
0.125 m/s,
m/s, aa few
few cracks
cracks were observed under tribo-corrosion conditions, while several
voids were generated beneath the sliding surface surface under
under mechanical
mechanical wear.
wear. With
With the
the rota-
rota-
tional velocity increasing, cracks nucleated and propagated into the subsurface under the
conditions of tribo-corrosion and mechanical wear. wear. Compared with the tribo-corrosion
tribo-corrosion
conditions, the the crack
crackpropagation
propagationwas wasmore
moreserious
seriousunder
under mechanical
mechanical wear, presenting
wear, presenting as
aasdeeper damaged location and a larger area of the fractured
a deeper damaged location and a larger area of the fractured region. region.
Metals 2022, 12,
Metals 2022,
Metals 2022, 12, 1503
12, xx FOR
FOR PEER
PEER REVIEW
REVIEW 666 of
of 12
of 12

Figure 5.
5. Damaged
Figure 5.
Figure Damaged surface
surface of
of Monel
Monel 400
400 alloy
alloy in
in conditions
conditions of
of (a)
(a) tribo-corrosion
tribo-corrosion and
and (b)
(b) mechanical
mechanical
wear under different rotational velocities of 0.125 m/s, 0.25 m/s, 0.375 m/s and 0.5 m/s in seawater.
wear under different rotational velocities of 0.125 m/s, 0.25 m/s, 0.375 m/s and 0.5 m/s inseawater.
wear under different rotational velocities of 0.125 m/s, 0.25 m/s, 0.375 m/s and 0.5 m/s in seawater.

Figure
Figure 6.6. The
The cross-section morphologies of Monel 400 alloy in
in conditions of
of (a) tribo-corrosion and
Figure 6. Thecross-section
cross-sectionmorphologies
morphologiesofof Monel
Monel400400
alloy
alloy conditions
in conditions (a)
of tribo-corrosion and
(a) tribo-corrosion
(b)
(b) mechanical
mechanical wear
wear under
under different
different rotational
rotational velocities
velocities of
of 0.125
0.125 m/s,
m/s, 0.25
0.25 m/s,
m/s, 0.375
0.375 m/s
m/s and
and 0.5
0.5
and (b) mechanical wear under different rotational velocities of 0.125 m/s, 0.25 m/s, 0.375 m/s and
m/s
m/s in
in seawater.
seawater.
0.5 m/s in seawater.
3.5. XPS
3.5. XPS Analysis
Analysis of of Corrosion
Corrosion Products
Products
Products
XPS
XPS analysis
XPS analysis
analysiswaswas conducted
conductedtoto
wasconducted reveal
toreveal
revealthe the
the chemical
chemical
chemical composition
composition
composition of
of corrosion
corrosion
of corrosion prod-
prod-
products
ucts
on on
uctsthe the
the Monel
onMonel Monel 400
400 alloy
400 alloy alloy
under under
under different
different
different conditions.
conditions.
conditions. FigureFigure
Figure 77 presents
7 presentspresents
the XPS the
the XPS
XPS spec-
spec-
spectrum
trum
of Ni of
trum of Ni
2p, NiCu2p,
2pCu
2p, and
Cu 2p
2pOand
and1s ofO
Othe1s
1s of the
the Monel
Monel
of 400
400 alloy
Monel 400 atalloy
alloythe at the
the original
original
at state and
original state and
stateafter
andthe after the
static
after the
static corrosion
corrosion and and tribo-corrosion
tribo-corrosion processes,
processes, respectively.
respectively. The The
peak
static corrosion and tribo-corrosion processes, respectively. The peak position, assignment peak position,
position, assignment
assignment and
and
and proportion
proportion are
are listed
are listed
proportion in Table
listed in
in Table
2. In the
Table 2.
2. In
O1s
In the
the O1s
O1s spectrum,
spectrum, the peaks
spectrum, the
the of O2− ,of
peaks
peaks ofOHO
O2−−, and
2− , OH
OH−−O–Cand O–C
and were
O–C
were
were located
locatedlocated at
at 531.2
at 531.2 eV,
eV, 531.6
eV, 531.6
531.2 eV and
531.6 eV and
and 532.4
eV 532.4 eV,
eV, respectively
eV, respectively
532.4 respectively [23–25].
[23–25]. In the
[23–25]. In the
In Ni
the2pNi
Ni3/2 2p 3/2 spectra,
spectra,
2p3/2 spectra,it
it
it was
waswas observed
observed
observed that
that
thatthethe
the NiNi species
Nispecies
specieswas was
wasthe the same
thesame under
sameunder
underthe the three
thethree conditions.
threeconditions.
conditions. The The
The peak
peak of
elemental
elemental
elemental Ni Ni was
Niwas detected
detectedatat
wasdetected 852.3
at852.3
852.3 eV,eV,
and
eV, and
thethe
and peaks
the peaks
peaks located
located at
at 856.2
at 856.2
located eV and
856.2 eV and
and 860.8
eV 860.8 eV were
860.8 eV
eV
were
indexedindexed
Ni(OH) Ni(OH)
were indexed Ni(OH) 2 and and
its its accompanying
accompanying peak, peak, respectively
respectively [26–28].
2 and its accompanying peak, respectively [26–28]. However, com-
2 [26–28].
However,However, com-
compared
with
paredthe
pared with
withoriginal
the state and
the original
original statestatic
state and corrosion,
and static
static the amount
corrosion,
corrosion, the
the amount of Niof
amount ofdecreased
Ni
Ni decreased
decreasedto 4.1%,to but but
to 4.1%,
4.1%, the
but
amount
the
the amount of
amount ofNi(OH)
of Ni(OH)
Ni(OH)2 increased
22 increased to
increased to 61.1%
to 61.1% after
61.1% after the
after the tribo-corrosion
the tribo-corrosion tests.
tribo-corrosion tests. For
tests. For the
For the Cu
the Cu 2p
Cu 2p
2p 3/2
3/2
3/2
spectra,
spectra, the
spectra, thebinding
the bindingenergies
binding energiesofof
energies CuO
of CuO
CuO andand
and Cu(OH)
Cu(OH)
Cu(OH) 2 were
22 were933.0
were eV eV
933.0
933.0 and
eV and 935.0
and eV, respectively.
935.0
935.0 eV,
eV, respec-
respec-
The peak
tively.
tively. Thelocated
The peak at 932.1at
peak located
located ateV belonged
932.1
932.1 eV to elemental
eV belonged
belonged to Cu or Cu
to elemental
elemental Cu2 O
Cu or[29–31].
or Cu
Cu22O According
O [29–31].
[29–31]. to the
According
According
Metals 2022, 12, x FOR PEER REVIEW 7 of 12
Metals 2022, 12, 1503 7 of 12

to the O1s spectra and the peak proportion listed in Table 3, it was deduced that Ni was
O1s spectra
oxidized to and the peak
Ni(OH) proportion listed in Table 3, it was deduced that Ni was oxidized
2 under both the static corrosion and tribo-corrosion conditions, while
to Ni(OH)2 under both the static corrosion and tribo-corrosion conditions, while Cu(OH)2
Cu(OH)2 was generated after the corrosion process, together with a larger amount of
was generated after the corrosion process, together with a larger amount of Cu2 O.
Cu2O.

Figure 7. The XPS spectra of Ni 2p, Cu 2p and O 1s detected for corrosion products formed under
Figure 7. The XPS spectra of Ni 2p, Cu 2p and O 1s detected for corrosion products formed under the
the (a) original state, (b) static corrosion and (c) tribo-corrosion conditions.
(a) original state, (b) static corrosion and (c) tribo-corrosion conditions.
Table 3. The assignment, binding energy and proportion of characteristic peaks from XPS analysis.
Table 3. The assignment, binding energy and proportion of characteristic peaks from XPS analysis.
Ni 2p3/2/Binding Cu 2p3/2/Binding O 1s/Binding
Samples Ni 2p3/2 /Binding Cu 2p3/2 /Binding O 1s/Binding
Samples Energy/Amount Energy/Amount Energy/Amount
Energy/Amount Energy/Amount Energy/Amount
852.3 15.5% Cu/Cu2O 932.1 12.9% O 2−
2− / /
Ni metal
Ni metal
852.3 15.5% Cu/Cu2 O 932.1 12.9% O− / /
Original
Original State Main 856.2
State Ni(OH)
Ni(OH)22 Main 856.2 43.8%
43.8% CuO
CuO 933.0
933.0 87.1%
87.1% OH
OH− 531.6
531.6 36.9%
36.9%
Sat.
Sat. 860.8
860.8 40.7%
40.7% Cu(OH)
Cu(OH)22 // // O-C
O-C 532.4
532.4 63.1%
63.1%
852.3
852.3 5.2%
5.2% Cu/Cu
Cu/Cu22O
O 932.1
932.1 45.5%
45.5% OO2−2− 531.2
531.2 17.1%
17.1%
Static Corro-
Static Nimetal
Ni metal
Corrosion Ni(OH) Main
Main 856.2
856.2 54.2%
54.2% CuO
CuO 933.0
933.0 23.7%
23.7% OH−−
OH 531.6
531.6 25.8%
25.8%
sion Ni(OH)22 Sat. 860.8 40.6% Cu(OH)2 935.0 30.8% O-C 532.4 57.1%
Sat. 860.8 40.6% Cu(OH)2 935.0 30.8% O-C 532.4 57.1%
Tribo-
Tribo-Corro-
Corrosion
Ni metal 852.3 4.1% Cu/Cu2 O 932.1 41.7% O2− 531.2 46.1%
Ni metal 852.3 4.1% Cu/Cu2O 932.1 41.7% O2− − 531.2 46.1%
sion Main 856.2 61.1% CuO 933.0 38.7% OH 531.6 18.2%
Ni(OH)2
Sat. 860.8 34.8% Cu(OH)2 935.0 19.6% O–C 532.4 35.7%
Main 856.2 61.1% CuO 933.0 38.7% OH − 531.6 18.2%
Ni(OH)2
Sat. 860.8 34.8% Cu(OH)2 935.0 19.6% O–C 532.4 35.7%
4. Discussion
4.1. Effect of Rotational Velocity on Mechanical Wear
4. Discussion
The influence
4.1. Effect of rotational
of Rotational Velocity onvelocity on the
Mechanical microstructure after mechanical wear was
Wear
explored by observing the subsurface morphologies of the Monel 400 alloy, and the typical
The influence of rotational velocity on the microstructure after mechanical wear was
TEM morphologies are presented in Figure 8. The rotational velocity had a significant effect
explored by observing the subsurface morphologies of the Monel 400 alloy, and the typi-
on the microstructure of the subsurface. As can be seen from Figure 8a, compared with
cal TEM morphologies are presented in Figure 8. The rotational velocity had a significant
the original grain size of the Monel 400 alloy (~100 nm), the grain size of the Monel 400
effect on the microstructure of the subsurface. As can be seen from Figure 8a, compared
alloy was significantly smaller (~25 nm) at the rotational velocity of 0.125 m/s, indicating
with the original grain size of the Monel 400 alloy (~100 nm), the grain size of the Monel
that grain refinement occurred in the subsurface of the Monel 400 alloy after undergoing
400 alloy was significantly smaller (~25 nm) at the rotational velocity of 0.125 m/s, indicat-
plastic deformation. However, at the rotational velocity of 0.5 m/s, the subsurface of the
ing that
Monel 400grain
alloyrefinement occurred elongated
exhibited extremely in the subsurface of the
grains, and fineMonel
grains400 alloy
only afternear
existed under-
the
going plastic
damaged surface. deformation. However, at the rotational velocity of 0.5 m/s, the subsurface
of the Monel 400 alloy exhibited extremely elongated grains, and fine grains only existed
near the damaged surface.
Metals 2022,12,
Metals2022, 12,1503
x FOR PEER REVIEW 88 of
of1212

Figure8.8.TEM
Figure TEM morphologies
morphologies of
of Monel
Monel 400
400 alloy
alloy after
aftermechanical
mechanicalwear
weartests
testsatat(a)
(a)0.125
0.125m/s
m/sand (b)
and
0.5 m/s.
(b) 0.5 m/s.

Fromthe
From themechanical-wear
mechanical-wear perspective,
perspective, thethe maximum
maximum contact
contact stress
stress waswas calculated
calculated as
as ~2.2 GPa based on the Hertz theory, as in spherical pin/ring contact,
~2.2 GPa based on the Hertz theory, as in spherical pin/ring contact, which is approximately which is approxi-
mately
10 times10 timesthan
larger largerthethan thestress
yield yieldof stress
Monelof Monel 400 (typically
400 (typically 283 MPa). 283 MPa).
It meansIt means
that thethat
the Monel
Monel 400 alloy
400 alloy would would
suffersuffer
severesevere
plasticplastic deformation
deformation under under this condition.
this condition. During During
the
the process
process of plastic
of plastic deformation,
deformation, partpart of the
of the mechanical
mechanical energy
energy was was storedininthe
stored themetallic
metallic
matrix,in
matrix, in the
the form of dislocation,
dislocation, withwithaamedium
mediumvalue valueofofthethestacking
stacking fault
faultenergy
energy of the
of
Monel
the Monel400400alloy in the
alloy in range of 80–128
the range mJ/mmJ/m
of 80–128 2, even2under
, even the
underlubricating effect of effect
the lubricating seawater of
seawater [32,33]. under
[32,33]. Firstly, Firstly,theunder the of
action action
shearofstress,
shear stress, grain reorientation
grain reorientation results results
in grainin grain
elon-
elongation
gation in the in the shear
shear direction.
direction. At the
At the samesametime,time, there
there areare
many many dislocations
dislocations around
around the
the elongated
elongated graingrain boundary,
boundary, andandthethe slipping
slipping of dislocations
of dislocations caused
caused by by severe
severe plastic
plastic de-
deformation
formation led ledtotothetherupture
ruptureofofthe theelongated
elongated grain.
grain. Next,
Next, thethe elongated
elongated grains
grains were
were re-
refined
fined totoform
formnanocrystalline
nanocrystalline [34,35].
[34,35]. AtAt aa higher rotational velocity,
velocity, the the wear
wearisismainly
mainly
controlled
controlledbybyplastic
plastic deformation
deformation peeling
peeling andandfatigue fracture,
fatigue which
fracture, whichrapidly consumes
rapidly consumes the
nanocrystalline layer on the surface. Therefore, at rotational velocity
the nanocrystalline layer on the surface. Therefore, at rotational velocity of 0.5 m/s, only a of 0.5 m/s, only a few
refined grainsgrains
few refined were wereobserved on theon
observed subsurface
the subsurfaceof theof Monel 400 alloy.
the Monel 400 alloy.
In
Inaddition,
addition,from fromthe thequantitative
quantitativemeasurement
measurementofoftribo-corrosion
tribo-corrosioncomponentscomponentsatat
various
variousvelocities
velocitiesshown shownin inFigure
Figure4,4,ititwas
wasrevealed
revealedthat thatthe
thetotal
totalmaterial
materialloss loss(T)(T)waswas
mainly determined by the additive of mechanical wear (W
mainly determined by the additive of mechanical wear (W0) and corrosion-accelerated0 ) and corrosion-accelerated
wear
wear(∆W
(ΔWc ). The exact values of T, W 00 and
c). The exact values of T, W and ∆WΔWcc increased
increased as as the
the increasing
increasing velocity,
velocity,and, and,
thus,
thus, the sliding distance increased. However, as shown in Figure 9, it was revealedthat
the sliding distance increased. However, as shown in Figure 9, it was revealed that
the
theincreased
increasedvalue valueofofTTand andWW0 0, ,with
withthe thedistance
distanceper percycle
cycleremaining
remainingconstant,
constant,indicates
indicates
that
thatthe
the microscopic
microscopic accelerated
accelerated wearwear losslossatataahigher
highervelocity
velocityis is mainly
mainly thethe result
result of
of the
Metals 2022, 12, x FOR PEER REVIEW
1503 9 9of
of 12

the accumulation
accumulation ofsliding
of the the sliding distance,
distance, and elongated
and elongated grainsgrains were observed
were observed at higher
at higher veloc-
velocities.
ities.

Figure 9.
9. The
Thematerial
materialloss rate
loss perper
rate cycle after
cycle tribo-corrosion
after and and
tribo-corrosion mechanical wearwear
mechanical at various rota-
at various
tional velocities.
rotational velocities.

4.2. Effect
4.2. Effect of
of Rotational
Rotational Velocity
Velocity onon Corrosion
Corrosion
From the
From theabove
aboveresults,
results,it it
cancan
be be concluded
concluded thatthat
the the corrosion
corrosion of theofMonel
the Monel 400
400 alloy
alloy in artificial seawater inhibited the mechanical wear to different
in artificial seawater inhibited the mechanical wear to different extents, which was mainly extents, which was
mainly dependent
dependent on the excellent
on the excellent lubricating lubricating
performance performance of the product’s
of the corrosion corrosion layer.
product’s
Ac-
layer. According to our previous study [22], nanoscale copper-rich
cording to our previous study [22], nanoscale copper-rich particles were produced particles were produced
in situ
in situ
on on thesurface
the worn worn surface of the400
of the Monel Monel
alloy,400 alloy,
which which
was was attributed
attributed to thecorrosion
to the selective selective
corrosion
of of nickel
nickel during during
the the tribo-corrosion
tribo-corrosion tests. The tests. The copper-rich
copper-rich grainsextruded
grains were were extruded
under
under cyclic shear stress and gradually evolved into a discontinuous
cyclic shear stress and gradually evolved into a discontinuous corrosion product’s corrosion product’s
layer.
layer. Owing to the excellent lubrication of the corrosion product’s layer, the shear stress
Owing to the excellent lubrication of the corrosion product’s layer, the shear stress during
during the friction process was greatly weakened, leading to lower material loss and a
the friction process was greatly weakened, leading to lower material loss and a lower fric-
lower friction coefficient after the tribo-corrosion tests than after the mechanical wear tests.
tion coefficient after the tribo-corrosion tests than after the mechanical wear tests.
The tribo-corrosion behavior of the Monel 400 alloy was influenced remarkably by the
The tribo-corrosion behavior of the Monel 400 alloy was influenced remarkably by
rotational velocity. The material loss rate and friction coefficient after both tribo-corrosion
the rotational velocity. The material loss rate and friction coefficient after both tribo-cor-
and mechanical wear tests increased, with the rotational velocities ranging from 0.125 m/s
rosion and mechanical wear tests increased, with the rotational velocities ranging from
to 0.5 m/s. Figure 10 depicts the TEM morphologies of the Monel 400 alloy after tribo-
0.125 m/s to 0.5 m/s. Figure 10 depicts the TEM morphologies of the Monel 400 alloy after
corrosion tests at 0.125 m/s and 0.5 m/s. The corrosion products’ layer on the worn
tribo-corrosion tests at 0.125 m/s and 0.5 m/s. The corrosion products’ layer on the worn
surface was observed. Spot-scanning results revealed that the chemical composition of
surface was observed. Spot-scanning results revealed that the chemical composition of the
the corrosion product’s layer was mainly Cu, which was consistent with our previous
corrosion product’s layer was mainly Cu, which was consistent with our previous re-
research. However, the thickness of the corrosion product’s layer decreased from 50 nm to
search.
30 nm as However,
the velocitythe increased
thickness fromof the0.125
corrosion
m/s to product’s
0.5 m/s. layer decreasedoffrom
The evolution 50 nm to
the corrosion
30 nm as the velocity increased from 0.125 m/s to 0.5 m/s. The evolution
product’s thickness was clearly controlled by the process of passivation and repassivation of the corrosion
product’s
competition thickness was clearly
[36]. Mischler controlled
et al. observedbythe thesame
process of passivation
behavior and repassivation
after tribo-corrosion tests,
competition [36]. Mischler et al. observed the same behavior
when AISI 430 steel sliding against an alumina ball was held at a passive potential after tribo-corrosion tests,
in
when
H2 SO4AISI[37]. 430
Thissteel slidingcan
evolution against an alumina
be explained by theball
truthwas held
that the at a passive
corrosion potential
product’s in
layer
H
was2SO4 [37]. This evolution can be explained by the truth that the corrosion product’s layer
continuously removed and exposed the matrix area where the corrosion took place at
was continuously
a higher rate whenremoved and exposed
the rotational velocity the matrix[38],
increased areawhich
whereisthe corrosion
confirmed bytook
Figureplace
4a.
at a higher
It can rate when
be observed thatthetherotational
degree ofvelocity
mechanical increased [38], which the
wear accelerated is confirmed
increased by Figure
corrosion
4a.
(∆CItw )can
withbethe
observed
velocity that the degree
increasing, of mechanical
indicating wear accelerated
that, although the increased
the thickness corro-
of the corrosion
sion (ΔC ) with the velocity increasing, indicating that, although the
product’s layer thinned with the rotational velocity increasing, it still allowed the Monel
w thickness of the cor-
rosion product’s layer thinned with the rotational velocity
400 alloy to completely repassivate, even at the maximum rotational velocity. increasing, it still allowed the
Monel 400 alloy to completely repassivate, even at the maximum rotational velocity.
Metals2022,
Metals 2022,12,
12,1503
x FOR PEER REVIEW 10
10 of 12
12

Figure10.
Figure 10. TEM
TEM images
images of
of the
the Monel
Monel 400400 alloy
alloy and
and the
the chemical
chemical composition
composition of
of corrosion
corrosion product’s
product’s
layer after tribo-corrosion tests at (a) 0.125 m/s and (b) 0.5 m/s.
layer after tribo-corrosion tests at (a) 0.125 m/s and (b) 0.5 m/s.

5. Conclusions
5. Conclusions
The influence
The influenceof of rotational
rotationalvelocities
velocitieson
onthe
the tribo-corrosion
tribo-corrosionbehavior
behaviorof
ofthe
theMonel
Monel 400
400
alloyin
alloy inartificial
artificialseawater
seawaterwas wasinvestigated.
investigated.
TheThe components
components of mechanical
of mechanical wear,
wear, corro-
corrosion
sionwear-corrosion
and and wear-corrosion interaction
interaction were were quantitatively
quantitatively determined.
determined. The results
The results revealed
revealed that
the tribo-corrosion behavior was highly dependent on the rotational velocity.
that the tribo-corrosion behavior was highly dependent on the rotational velocity. The The specific
conclusions are listedare
specific conclusions as listed
follows:as follows:
1.
1. The total material loss and friction coefficient increased with the increasing velocity,
presenting as
presenting asdelamination
delaminationalongside
alongside thethe sliding
sliding direction
direction atsurface
at the the surface
and theand the
crack
crack nucleation
nucleation and propagation
and propagation at the at the subsurface.
subsurface.
2.
2. Compared with mechanical wear, wear, the
the damage
damage induced
induced byby tribo-corrosion
tribo-corrosion was was much
much
corrosion product’s
lower due to the formation of the corrosion product’s layer
layer inin aa thickness
thickness of of several
several
tens of nanometers, exhibiting excellent lubricating performance.
performance.
3.
3. After the mechanical wear tests, the increased material material loss
loss rate
rate with
with the
the increasing
increasing
velocity was mainly the resultresult of
of the
the accumulation
accumulation of of the
the sliding
sliding distance.
distance.
4.
4. Since the thickness
thickness of ofthe
thecorrosion
corrosionproduct’s
product’slayer
layerdecreases
decreasesfromfrom5050 nmnmtoto3030nm nmas
as the velocity increases from 0.125 m/s to 0.5 m/s, the material loss
the velocity increases from 0.125 m/s to 0.5 m/s, the material loss rate after the tribo- rate after the
tribo-corrosion testsincreases
corrosion tests also also increases
with thewith the velocities
velocities increasing,
increasing, possibly possibly
due to due to the
the rebuilt
rebuilt balance between the passivation and slowed repassivation
balance between the passivation and slowed repassivation at higher velocities. at higher velocities.
Metals 2022, 12, 1503 11 of 12

Author Contributions: Resources, J.W. and F.Y.; conceptualization, Y.Z. and J.W.; methodology,
Y.Z.; validation, Y.Z.; writing—original draft preparation, Y.Z.; supervision, J.W. and H.L.; writing—
review and editing, J.W., H.L. and F.Y. All authors have read and agreed to the published version of
the manuscript.
Funding: This work was financially supported by the National Key Research and Development
Program of China (No. 2021YFB3400400).
Data Availability Statement: The raw/processed data required to reproduce these findings cannot
be shared at this time, as the data also form part of an ongoing study.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Wang, C.; Wang, S.; Wang, H.; Ruan, G.; Xiao, Y.; Jiang, Z.; Li, X. Research status and prospects of tribological behaviors of key
friction pairs of materials in marine equipment. Mater. Sci.-Medzg. 2021, 27, 148–154. [CrossRef]
2. Li, R.; Wen, C.; Meng, X.; Xie, Y. Measurement of the friction force of sliding friction pairs in low-speed marine diesel engines and
comparison with numerical simulation. Appl. Ocean. Res. 2022, 121, 103089. [CrossRef]
3. Liang, Y.; Gao, D.; Chen, B.; Zhao, J. Friction and wear study on friction pairs with a biomimetic non-smooth surface of 316L
relative to CF/PEEK under a seawater lubricated condition. Chin. J. Mech. Eng. 2019, 32, 66. [CrossRef]
4. Yuan, S.J.; Pehkonen, S.O. Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing
simulated seawater. Corros. Sci. 2007, 49, 1276–1304. [CrossRef]
5. Marenych, O.; Kostryzhev, A. Strengthening Mechanisms in Nickel-Copper Alloys: A Review. Metals 2020, 10, 1358. [CrossRef]
6. Jiang, W.; Zhu, S.; Wang, S. Effect of sliding speed and hardness on wear behavior and mechanism of AISI H13 steel. Proc. Inst.
Mech. Eng. Part J J. Eng. Tribol. 2020, 234, 1822–1833. [CrossRef]
7. Mahmud, D.N.F.; Bin Abdollah, M.F.; Bin Masripan, N.A.; Tamaldin, N.; Amiruddin, H. Influence of contact pressure and sliding
speed dependence on the tribological characteristics of an activated carbon-epoxy composite derived from palm kernel under dry
sliding conditions. Friction 2019, 7, 227–236. [CrossRef]
8. Hedenqvist, P.; Olsson, M. Sliding Wear Testing of Coated Cutting-Tool Materials. Tribol. Int. 1991, 24, 143–150. [CrossRef]
9. Henry, P.; Takadoum, J.; Bercot, P. Depassivation of some metals by sliding friction. Corros. Sci. 2011, 53, 320–328. [CrossRef]
10. Chen, J.; Yan, F. Corrosive Wear Performance of Monel K500 Alloy in Artificial Seawater. Tribol. Trans. 2013, 56, 848–856.
[CrossRef]
11. Mischler, S.; Debaud, S.; Landolt, D. Wear-accelerated corrosion of passive metals in tribocorrosion systems. J. Electrochem. Soc.
1998, 145, 750–758. [CrossRef]
12. Obadele, B.A.; Andrews, A.; Shongwe, M.B.; Olubambi, P.A. Tribocorrosion behaviours of AISI 310 and AISI 316 austenitic
stainless steels in 3.5% NaCl solution. Mater. Chem. Phys. 2016, 171, 239–246. [CrossRef]
13. Xu, Y.D.; Qi, J.H.; Nutter, J.; Sharp, J.; Bai, M.W.; Ma, L.; Rainforth, W.M. Correlation between the formation of tribofilm and
repassivation in biomedical titanium alloys during tribocorrosion. Tribol. Int. 2021, 163, 107147. [CrossRef]
14. Chen, H.; Zhang, Z.; Hao, X.H.; Huang, B.X.; Zhao, X.C.; Hu, C.C. Microstructure and tribocorrosion properties of NiTi/AlNi2Ti
ternary intermetallic alloy. Vacuum 2021, 184, 109928. [CrossRef]
15. Kossman, S.; Coelho, L.B.; Mejias, A.; Montagne, A.; Van Gorp, A.; Coorevits, T.; Touzin, M.; Poorteman, M.; Olivier, M.G.; Iost,
A.; et al. Impact of industrially applied surface finishing processes on tribocorrosion performance of 316L stainless steel. Wear
2020, 456, 203341. [CrossRef]
16. Ziomek-Moroz, M.; Miller, A.; Hawk, J.; Cadien, K.; Li, D.Y. An overview of corrosion-wear interaction for planarizing metallic
thin films. Wear 2003, 255, 869–874. [CrossRef]
17. Liu, M.; Wang, Z.G.; Shi, C.B.; Wang, L.W.; Xue, X.D. Corrosion and wear behavior of Ti-30Zr alloy for dental implants. Mater.
Res. Express 2019, 6, 0865c8. [CrossRef]
18. Namus, R.; Nutter, J.; Qi, J.; Rainforth, W.M. Sliding speed influence on the tribo-corrosion behaviour of Ti6Al4V alloy in
simulated body fluid. Tribol. Int. 2021, 160, 107023. [CrossRef]
19. Bi, Q.; Liu, W.; Ma, J.; Yang, J.; Pu, Y.; Xue, Q. Tribocorrosion behavior of Ni-17.5Si-29.3Cr alloy in sulfuric acid solution. Tribol. Int.
2009, 42, 1081–1087. [CrossRef]
20. Ferreira, D.F.; Ale Almeida, S.M.; Soares, R.B.; Juliani, L.; Bracarense, A.Q.; Cunha Lins, V.d.F.; Rabelo Junqueira, R.M. Synergism
between mechanical wear and corrosion on tribocorrosion of a titanium alloy in a Ringer solution. J. Mater. Res. Technol. 2019, 8,
1593–1600. [CrossRef]
21. Zhu, Y.; Liu, H.; Zhang, D.; Wang, J.; Yan, F. Effect of polarization potentials on tribocorrosion behavior of Monel 400 alloy in
seawater environment. Tribol. Int. 2022, 168, 107445. [CrossRef]
22. Zhu, Y.H.; Liu, H.; Wang, J.Z.; Yan, F.Y. Antagonistic effect of electrochemical corrosion on the mechanical wear of Monel 400
alloy in seawater. Corros. Sci. 2022, 198, 110120. [CrossRef]
23. Ayiania, M.; Smith, M.; Hensley, A.J.R.; Scudiero, L.; McEwen, J.-S.; Garcia-Perez, M. Deconvoluting the XPS spectra for
nitrogen-doped chars: An analysis from first principles. Carbon 2020, 162, 528–544. [CrossRef]
Metals 2022, 12, 1503 12 of 12

24. Lee, E.; Lee, C.E.; Han, J.H. Effects of proton irradiation on single-stranded DNA studied by using X-ray photoelectron
spectroscopy. J. Korean Phys. Soc. 2016, 69, 578–583. [CrossRef]
25. Okada, K.; Kotani, A. Oxygen is core-level photoemission as a tool to investigate the unoccupied electronic states of cuprates. J.
Phys. Soc. Jpn. 2006, 75, 123703. [CrossRef]
26. Chen, W.; Chu, M.; Gao, L.; Mao, L.; Yuan, J.; Shangguan, W. Ni(OH)(2) loaded on TaON for enhancing photocatalytic water
splitting activity under visible light irradiation. Appl. Surf. Sci. 2015, 324, 432–437. [CrossRef]
27. Jeong, D.J.; Kim, W.S.; Choi, Y.K.; Sung, Y.E. Intercalation/deinterealation characteristics of electrodeposited and anodized nickel
thin film on ITO electrode in aqueous and nonaqueous electrolytes. J. Electroanal. Chem. 2001, 511, 79–87. [CrossRef]
28. Wang, W.; Wang, W.; Wang, M.; Guo, X. Facile In Situ Synthesis of Hierarchical Porous Ni/Ni(OH)(2) Hybrid Sponges with
Excellent Electrochemical Energy-Storage Performances for Supercapacitors. Chem. Asian J. 2014, 9, 2590–2596. [CrossRef]
29. Tao, Z.; Gu, J.; Fang, H.; Chen, L.; Chen, J. Cu doped epsilon-Fe2-3N films with manipulable magnetic and transport properties.
Mater. Lett. 2019, 250, 131–134. [CrossRef]
30. Arun, L.; Karthikeyan, C.; Philip, D.; Sasikumar, M.; Elanthamilan, E.; Merlin, J.P.; Unni, C. Effect of Ni2+ doping on chemocatalytic
and supercapacitor performance of biosynthesized nanostructured CuO. J. Mater. Sci.-Mater. Electron. 2018, 29, 21180–21193.
[CrossRef]
31. Pinon-Espitia, M.; Lardizabal-Gutierrez, D.; Camacho-Rios, M.L.; Herrera-Perez, G.; Ochoa-Lara, M.T. Electronic structure
comparison of Cu 2p and O 1s X-Ray photoelectron spectra for CuxO nanofibers (x = 1, 2, i). Mater. Chem. Phys. 2021, 272, 124981.
[CrossRef]
32. Hansen, N.; Jensen, D.J. Development of microstructure in FCC metals during cold work. Philos. Trans. R. Soc. A-Math. Phys. Eng.
Sci. 1999, 357, 1447–1469. [CrossRef]
33. Ebrahimi, G.R.; Momeni, A.; Ezatpour, H.R.; Jahazi, M.; Bocher, P. Dynamic recrystallization in Mone1400 Ni-Cu alloy: Mechanism
and role of twinning. Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process. 2019, 744, 376–385. [CrossRef]
34. Singh, J.B.; Cai, W.; Bellon, P. Dry sliding of Cu-15 wt%Ni-8 wt%Sn bronze: Wear behaviour and micro structures. Wear 2007, 263,
830–841. [CrossRef]
35. Roncery, L.M.; Jacome, L.A.; Aghajani, A.; Theisen, W.; Weber, S. Subsurface characterization of high-strength high-interstitial
austenitic steels after impact wear. Wear 2018, 402, 137–147. [CrossRef]
36. Stemp, M.; Mischler, S.; Landolt, D. The effect of mechanical and electrochemical parameters on the tribocorrosion rate of stainless
steel in sulphuric acid. Wear 2003, 255, 466–475. [CrossRef]
37. Mischler, S. Triboelectrochemical techniques and interpretation methods in tribocorrosion: A comparative evaluation. Tribol. Int.
2008, 41, 573–583. [CrossRef]
38. Benea, L.; Ponthiaux, P.; Wenger, F.; Galland, J.; Hertz, D.; Malo, J.Y. Tribocorrosion of stellite 6 in sulphuric acid medium:
Electrochemical behaviour and wear. Wear 2004, 256, 948–953. [CrossRef]