Journal of Bio- and Tribo-Corrosion (2021) 7:83

https://doi.org/10.1007/s40735-021-00511-w

Wear‑Corrosion Synergy on Din‑16MnCr5 Steel Under Nitriding

and Post‑Oxidizing Treatments
W. D. Wong‑Ángel1 · J. Martínez‑Trinidad2 · I. Campos‑Silva2 · V. Hernandez‑Hernandez2 · U. S. Silva‑Rivera1 ·
R. A. García‑León2 

Received: 27 December 2020 / Revised: 14 March 2021 / Accepted: 30 March 2021

© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021

Abstract
New results about the wear-corrosion synergy behavior of nitrided DIN-16MnCr5 steel immersed in a saline solution were
obtained in this work. Tribocorrosion tests were performed on three different samples under ball-on-flat configuration: nitrid-
ing, nitriding plus post-oxidation, and untreated material using electrochemical polarization with an open-circuit potential in
a 5% NaCl solution. The sliding wear tests in the presence and absence of corrosion were developed under 20 N of normal
load, 2.5 mm of stroke length, 10 mm/s of speed, 100 m of total sliding distance, and ­Al2O3 balls of Ø = 4.8 mm that were
used as a counterpart according to the ASTM G119 standard procedure. The results showed that the presence of a magnetite
phase ­(Fe3O4) at the surface of the nitrided plus post-oxidation on DIN-16MnCr5 steel increased the wear-corrosion synergy
around ~ 5 times with respect to the untreated samples, which provides a potential solution to reduce the degradation impact
in mechanical components for navy military industry applications. However, the wear-corrosion synergy (T) contribution to
volume removal is higher than wear-corrosion (∆WC) by itself and also than the contribution of corrosion due to wear (∆CW).

Keywords  Tribocorrosion · Surface hardening · Nitriding · Saline solution · Failure mechanisms

Abbreviations W0 Rate of loss material with − 1 V protection.

T Tribocorrosion test W Total wear rate.
C0 Corrosion rate without wear. ∆WC Increase in the wear rate caused by corrosion.
CW Wear component in corrosion behavior. Ct Total corrosion rate.
K Constant (3272 mm g/A cm year). ∆CW Increase in the corrosion rate caused by wear.
Icorr Corrosion current density. VR Volume material removal.
EW Equivalent weight. A Exposed area.
ρ Density. t Test duration.
βa Anodic Tafel slope. OCP Open-circuit potential.
βc Cathodic Tafel slope. Ecorr Potential corrosion.
Rp Polarization resistance. CoF Friction coefficient.
S Synergy factor between wear and corrosion. U Untreated steel sample.
LT Total material loss. N Nitride sample.
NP Nitride plus post-oxidized sample

* J. Martínez‑Trinidad
jomartinezt@ipn.mx
1 Introduction
* R. A. García‑León
ragarcial@ufpso.edu.co
In recent years, the wear in metallic components operat-
1
SEDENA, D.G.E.M., Universidad del Ejército y Fuerza ing under corrosive and wear conditions has provoked an
Aérea, Escuela Militar de Ingenieros, Av. Industria Militar increase in research attention, giving rise to applying hard-
261, A.P. 53960 Mexico City, Mexico ening processes that can extend the operational life of such
2
Instituto Politécnico Nacional, Grupo Ingeniería de components. Due to the economic implications related to
Superficies, SEPI-ESIME, U.P. Adolfo López Mateos, wear-corrosion/tribocorrosion synergy, studies have focused
Zacatenco, A.P. 07738 Mexico City, Mexico

13
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 83   Page 2 of 13
on improving the mechanical and chemical properties of
elements used in essential applications (e.g., navy military
industry, due to the exposure to saline environments) [1, 2].
Under corrosive conditions, metallic components are sub-
ject to a friction (wear-corrosion) effect between mechani-
cal wear and chemical or electrochemical processes. Wear-
corrosion synergy, also called tribocorrosion phenomenon,
is present in many mechanical applications. It accelerates
material damage, compromising equipment security, and
could generate catastrophic failures and economic losses
[3]. During tribocorrosion, the volume removal in materi-
als is not a simple sum determined by mechanical wear and
corrosion, but some parameters, such as coatings, mechani-
cal contact, environment, and corrosion conditions, should
also be taken into account [4]. Thermochemical and surface
treatments have been used to reduce corrosion and improve
the wear rate of metallic components, thus improving the
useful life of the materials [5].
Studies related to the tribocorrosion tests have measured
additional corrosion due to wear by applying the ASTM
G119-09 standard methodology to examine wear-corro-
sion synergy [6]. The synergistic effect between the loss of
mechanical wear and electrochemical corrosion in materials
can be described as S = T–W0–C0, where the synergy factor
(S) between corrosion and wear is determined by the total
loss of material in the medium (T) minus the rate of lost
material due to wear with cathodic protection (W0) and the
corrosion rate without wear (C0) [7].
On the other hand, Zhang et al. [8] studied the behavior
of the AISI 1045 steel and AISI 2205 duplex stainless steel
under pin-on-disc configuration to elucidating the degrada-
tion due to tribocorrosion under corrosive environments.
The results showed that the interplay between chemical,
mechanical, and electrochemical processes aids both corro-
sion and corrosion due to wear, in consequence, significant
degradation of the material without coating. Also, high val-
ues of CoF and the destruction of the passive layer increased
material removal by wear. Eghlimi et al. [9] investigated
the tribocorrosion behavior of a super duplex stainless steel
under pin-on-disc configuration in NaCl solution. The results
demonstrated a significant effect of the applied potential on
the wear and corrosion synergy. Therefore, degradation and
material removal involve sequential wear and wear due to
corrosion. El-Aziz et al. [10] evaluated the tribocorrosion
behavior of the Al-Si alloy reinforced with A ­ l2O3 particles
on samples immersed in NaCl solution under pin-on-disc
configuration. The results revealed that a significant concen-
tration of A
­ l2O3 particles improves the corrosion resistance
influenced by the speed and wear values.
Tribocorrosion studies on nitride and post-oxidation
process materials are few. Fernandes et al. [11] reported
the influence of the nitride and nitride plus oxidation on
the tribocorrosion properties on a Ti6Al4V alloy under
13
Journal of Bio- and Tribo-Corrosion (2021) 7:83
NaCl solution and pin-on-disc configuration. The results
clearly show an improvement of the corrosion and wear
performance when the layer thickness increases, and there-
fore, the superficial hardness of the samples is influenced
by the processing conditions [12, 13]. Hacısalihoglu et al.
[14] studied the effect of plasma nitriding on corrosion,
wear, and tribocorrosion behavior on different types of
steels using a pin-on-disc configuration under NaCl solu-
tion. The results demonstrated that the nitriding improved
the corrosion and wear resistance and changed the elec-
trochemical in pitting and peaches failure mechanisms on
the surface [15].
In the case of studies on DIN-16MnCr5, Yegen and
Usta [16] evaluated the effect of salt bath cementation on
wear resistance and mechanical behavior of DIN-16MnCr5
steel. The results showed that the wear resistance of the
DIN-16MnCr5 steel increases with the cementation pro-
cess due to the improvement of the superficial hardness,
which increases with the exposure time. In the same way,
Brodyanski et  al. [17] studied the microstructural and
chemical changes during the application of load on the
DIN-16MnCr5 steel case hardened by various laboratory
methods. The results indicate that the thermal treatment
improved the superficial hardness around 3.5 times, simi-
lar to Ref. [18]. Due to the superficial treatment, a trans-
formation phase is provoked from γ-austenite to ε- and
α′-martensite, with the appearance of an oxidative layer
on the surface. Also, the authors demonstrate that during
sliding high residuals stresses appear (~ 10 GPa), which
was manifested in sub-surface elastic strains. Wong-Ángel
et al. [2] performed a tribocorrosion test on the carburized
samples of DIN-16MnCr5 immersed in a saline solution
under different test parameters. The results showed that the
carburized sample plus manganese coating increased the
tribocorrosion effect around 3.8 times due to the increase
of the superficial hardness.
Ceiari and Timelli [19] optimized the oxy-nitro-car-
burizing process on the DIN-16MnCr5 steel for industrial
components by reducing the processes. The results showed
that it is possible to increase the magnetite layer thickness
on the compound zone, increasing the temperature and
time of exposure under the ­N2O atmosphere, providing
improved wear and corrosion results.
In this work, new results about the wear-corrosion syn-
ergy on DIN-16MnCr5 steel were obtained on three dif-
ferent samples under ball-on-flat configuration: untreated
(U), nitriding (N), and nitriding plus post-oxidation pro-
cess (NP) immersed in a NaCl solution to evaluate the
mechanical–chemical behavior under marine saline condi-
tions for navy military industry applications, specifically
in alarm shutdown system, lock piece, and closer bracket
in weapons, which have not been reported in the open
literature.
Journal of Bio- and Tribo-Corrosion (2021) 7:83 Page 3 of 13  83

2 Experimental Details salt bath, sodium cyanate (NaCNO) is obtained as an active

Samples with a diameter of 19 mm and 4 mm thick, with a
characteristic hardness around ~ 2.1 GPa were used in this
study. The nominal chemical composition for DIN-16MnCr5
steel in (wt. %) is 0.17 C, 0.22 Si, 1.0 Nb, 0.95 Cr, and 0.20
Cu, using the atomic absorption spectrophotometer test [20].
The most relevant mechanical–physical properties of DIN-
16MnCr5 steel are shown in Table 1.
2.1 Thermochemical Processes
compound, which comes from the oxidation of sodium cya-
nide (NaCN) [24]. The reactions involved in the process are
the following:
2NaCN + O → 2NaCNO. (1.1)
Sodium cyanates (NaCNO) formed in reaction (1.1) can
form sodium carbonates ­(Na2CO3) by oxidation:
2NaCNO + O2 → Na2 CO3 + 2N + CO. (1.2)
Nitrogen diffuses and CO reacts with iron:

2.1.1 Nitriding (N) 2CO + Fe → FeC + CO2 . (1.3)

Nitriding is a thermochemical treatment that provides Nitro-
gen to the surface of the ferrous materials; this isothermal
process is used to generate layers with excellent wear and
corrosion resistance. The molten salt nitriding process is car-
ried out in a crucible container and consists of a liquid solu-
tion with cyanide salts. The most common components used
for thermochemical treatment is 60–70 wt% sodium cyanide
(NaCN) and 30–40 wt% potassium cyanide (KCN). This
process requires preheating the component to be nitrided to
420 °C and then entering it into a molten salt bath at 580 °C
for a period that depends directly on the composition of the
material and the layer thickness required to be obtained. In
this way, the (N) treatment was performed at 580 °C for 6 h
according to the considerations reported by Funatani [24].
The nitrogen diffusion on the surface of the ferrous mate-
rial generates a compound zone following a diffusion zone
that consists of an iron matrix with nitrites precipitated that
react with the alloying elements. This phase depends on the
treatment conditions and the efficacy of the nitriding agent.
During this process, when the sample is immersed in the
Table 1  Relevant mechanical–physical properties of DIN-16MnCr5
steel
Property Value
CO2 + NaCN → NaCNO + CO. (1.4)
2.1.2 Nitriding Plus Post‑Oxidizing Process (NP)
The post-oxidation process consists mainly of six steps: (1)
degreasing, (2) preheating, (3) nitriding, (4) oxidant, (5)
washing, and finally (6) oil immersion [25]. The samples
must be previously preheated to a temperature of around
380 °C as usual in salt bath treatments. In this way, nitriding
is generally carried out between 30 and 120 min at 580 °C
(TF1 salt bath). Subsequently, the samples are introduced
into the oxidizing bath (Salt Bath AB1) at a temperature of
420 °C for 20 to 30 min; finally, the samples are placed in an
oil wash bath. Note that if after nitriding the surface of the
parts is too rough, mechanical polishing can be applied; this
process has been widely described in the literature [26, 27].
In the post-oxidizing process, some (N) samples were
exposed to an (NP) process with post-oxidation in a
nitrate–nitrite salt bath AB1 at 420 °C for 20 min and then
cooled in water to room temperature, taking into account the
considerations reported by Boßlet and Kreutz [28].
2.2 Corrosion‑Wear Synergy Tests

Thermal conductivity  ~ 46 W/mK Tests were performed in a saline solution (5% NaCl) using a
Poisson coefficient 0.27–0.30 Bruker/UMT-2 (Fig. 1), connected to three-electrode chemi-
Shear modulus 80 GPa cal cells, with a ball-on-flat configuration. The samples
Yield strength 415 MPa before the tribocorrosion tests presented a surface rough-
Tensile strength 520 MPa (800–1100 N/mm2) ness of ~ 0.048 μm. In this way, electrochemical tests were
Hardness (H) 1.5–2.1 GPa obtained at room temperature using an Ag/AgCl as a refer-
Carburizing 860–980 °C (H = 7.4 GPa) ence electrode, a platinum wire as a counter electrode, U,
Nitriding 420 °C N and 580 °C BS N, and NP as a working electrode, a scan speed of 0.8 mV/s,
Nitriding plus post oxidation (H =  ~ 6.04 GPa) and and an area exposed to the saline solution of 150 ­mm2. Tests
(H =  ~ 6.68 GPa, reported in this
study) were performed under a load of 20 N, a stroke length of
Case hardening 780–820 °C (H =  ~ 7.0 GPa) 2.5 mm, a speed of 10 mm/s, a total sliding distance of
Soft annealing 650–700 °C/furnace (H = 2.4 GPa) 100 m, and ­Al2O3 balls of Ø = 4.8 mm that were used as a
counterpart, for a total test duration of 2.08 h. Finally, each
Source: [21–23]

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polarization resistance ­R P is obtained directly from the

linear polarization diagram, using the Stern and Geary
equation (Icorr = B/RP), which relates the slope to corrosion
rate and Tafel slopes:
𝛽a 𝛽c
Icorr =
2.303 × (𝛽a + 𝛽c ) × Rp (2)

On the other hand, according to the ASTM G119-09

standard procedure the synergistic effects (S) of mechani-
cal and electrochemical material loss are described by
Eq. 3, and the material removal ­W0 with cathodic protec-
tion is calculated using Eq. 4:
S = LT −W0 −C0 (3)

VR
W0 = (4)
A×t
Fig. 1  Tribocorrosion test equipment scheme The total material removal due to wear ­(W0) was esti-
mated for the samples using Eq. 4, and thus, the E
­ OCP was
obtained before, during and after the tribocorrosion tests.
experimental condition was replicated at least three times to The regimes of wear-corrosion are estimated using the
guarantee the statistical results. following ratios:
ΔCw
The wear dominated regime is < 0.1,
2.3 Tribocorrosion Equations ΔW c

Tribocorrosion tests were developed according to the ΔCw

experimental parameters described in Sect. 2.2, following The wear − corrosion regime is 0.1 ≤
ΔWc
< 1,
the ASTM G119-09 standard procedure guidelines [6]. The
corrosion tests were calculated without wear ­(C0), and wear
ΔCw
with corrosion (CW). In the case of wear tests without cor- The corrosion dominated regime is ≥ 1.
rosion, a protection of − 1 V of the open-circuit potential ΔWc
for (W0) was applied, thus avoiding the influence of corro-
Moreover, for the W 0 and T = L T tests, the CoF was
sion on both materials, this value has been used by several
recorded continually with the aid of the CTR software
authors in the literature [29–31]; likewise, the mechanical
of the UMT-2 equipment. During the test, CW, W0, and T,
wear (WC), was calculated taking into account the volume
the material removal of the worn tracks were obtained by
of material removal, and finally, tribocorrosion (T) was esti-
non-contact profilometry using a Bruker/GT-K 3D. The
mated under-recorded conditions. In conclusion, four tests
microstructures of N and NP samples were obtained via
were conducted (two corrosion tests, C0 and CW, and two
optical microscope using an Olympus/GX51, and worn
wear tests, W0 and T). In this way, the following equations
tracks were analyzed by scanning electron microscopy
were used:
with JEOL/JSM-7800F/SEM operating at 25  kV. The
The determination of corrosion rate during linear polari-
phase’s identification was analyzed by the X-ray diffrac-
zation in the absence of wear (C0) and corrosion with wear
tion technique with Bruker/D8-ADVANCE/XRD using a
loss rate (CW) was estimated to the three samples (U, N, and
normal scan, Cu-Kα radiation and 2θ range of 10°–100°.
NP) using the Faraday expression (Eq. 1):
Finally, the superficial hardness was measured using a Shi-
K × Icorr × EW madzu/HMV-G21 equipment.
C = C0 = CW = (1)
𝜌

The corrosion current density (Icorr) was calculated

in the range of 200  mV below the OCP to 200  mV,
with the OCP in 500 s intervals for a total test time of
7500 s, according to the ASTM G3-89, using Eq. 2. The

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Journal of Bio- and Tribo-Corrosion (2021) 7:83 Page 5 of 13  83

3 Results and Discussions
3.1 Microstructure and Mechanical Properties
of the N and NP Samples
Figure 2a and b shows a layer thickness of ~ 25 and ~ 22 μm
with a surface hardness of 6.04 and 6.68 GPa for N and
NP, respectively. Figure 2c shows the XRD pattern for the
treated samples revealed the presence of F ­ e3O4, ε-Fe3N,
and a compound layer, indicating that the surface layer is
mainly composed of ε-Fe3N, which provides a higher hard-
ness and excellent wear resistance [32]. The main differ-
ence between the two treatments N and NP is the forma-
tion of ­Fe3O4 phase, thus improving the corrosion and wear
resistance in a better way [33, 34]. Notice that, from Table 1,
the mechanical–physical properties of the DIN-16MnCr5
can be improved with the use of different thermal treatments
and methods of cooling that increase the superficial hard-
ness (2, 3, even four times more), and therefore the wear
and corrosive protection under different environments and
test conditions.
3.2 Electrochemical Corrosion
The corrosion current density values (I corr) were deter-
mined with Tafel extrapolation (potentiodynamic polariza-
tion curves) using Eq. 2, considering also a linear region
of 20 mV for U, N, and NP samples before and after the

Fig. 2  Cross-sectional view of the microstructure for (a) N sample, (b) NP sample, and (c) XRD pattern

13
 83   Page 6 of 13 Journal of Bio- and Tribo-Corrosion (2021) 7:83

Fig. 3  Potentiodynamic polarization curves; (a) C0, and (b) CW tests

Table 2  Wear loss rates obtained from electrochemical tests

Condition Ecorr Icorr (μA/cm2) Rp βa (mV/decade) βc Wear loss rate (mm/year)
(mV Vs Ag/AgCl) (Ω ­cm2) (mV/decade)

Electrochemical test without wear—C0

U  − 410.39 ± 28 4.98 ± 0.009 1001.90 ± 90.0 37.60 ± 3.0 110.2 ± 9.0 0.0808 ± 0.0015
N  − 284.56 ± 19 6.44 ± 0.017 8540.50 ± 17.1 98.60 ± 2.3 63.30 ± 3.7 0.0011 ± 0.0012
NP 112.09 ± 10 7.21 ± 0.009 31,238.2 ± 89.9 131.8 ± 5.6 155.3 ± 4.2 0.0001 ± 0.0010
Electrochemical test with wear—CW
U  − 423.25 ± 27 6.25 ± 0.009 1218.82 ± 89.2 51.6 ± 3.0 111.3 ± 10.0 0.0246 ± 0.0026
N  − 242.90 ± 22 5.24 ± 0.017 2028.47 ± 17.0 46.7 ± 3.6 29.5 ± 2.2 0.0092 ± 0.0010
NP  − 193.70 ± 15 5.14 ± 0.017 7089.47 ± 47.0 87.2 ± 6.9 84.6 ± 7.1 0.0049 ± 0.0005

Fig. 4  OCP behavior before,

during, and after the wear test

tribocorrosion test (Fig. 3a and b). Table 2 shows the sum- 20  N load during wear, displacing the potentiodynamic
marized results. polarization curves on the lower end. The NP condition at
The potential becomes significantly negative under all 0.99 µA ­cm2 (Fig. 2a) implies that the coating maintains
conditions, since the tribocorrosion test featured an applied excellent resistance to corrosion in the 5% NaCl solution

13
Journal of Bio- and Tribo-Corrosion (2021) 7:83 Page 7 of 13  83
in the test without wear (C0). However, when the load is
applied over the surface, the corrosion current density
increases by a factor of ­101–102 [35].
3.3 Friction and Wear Behavior
Volume removal in mechanical components is due to differ-
ent mechanisms of W0 and CW [36]. From Fig. 4, the poten-
tial in the medium was measured to determine behavior,
observing a drop (zone 1) in the chart shown in Fig. 5 due
to the removal of de-passivation films formed in the samples.
In zone 2, the active metal footprint left by the action of the
alumina ball over the sample is more prone to accelerated
corrosion due to wear. In zone 3, the alumina ball ceased to
act over the surface, and the passive film was formed again.
The second mechanism is due to the metal particles detached
due to the action of the shank with the ­Al2O3 alumina ball on
the metal surface. Note that OCP showed a decrease for the
three samples in zone 1; thus, the U sample released nega-
tive values (~ 350 V) when the test started. In the opposite
case, the N and UP shown positive values of around ~ 150 V.
During the tests (Zone 2), OCP values are constant due to
Fig. 5  Wear tracks in the (a) C0 and (b) CW tests
Fig. 6  CoF for (a) C0, and (b) CW tests
the material removal through mechanical contact and repas-
sivation of the passive layer; in the final tests the OCP values
reached negative values.
The results of volume removal during the ­W0 test were
calculated via optical profilometry, obtaining depths of
around 30, 14, and 3 µm for U, N, and UP, respectively,
as it is shown in Fig. 5a and b. These values are directly
influenced by the superficial hardness obtained through the
thermochemical processes of nitriding and nitriding plus
post-oxidizing.
The corrosion products developed on the worn tracks can
change the CoF and W0. In the case of the W0 test, CoF was
between 0.35 and 0.40, but in the case of the CW, a low
value was obtained between 0.25 and 0.42. For W0 on NP
samples, the lower adhesion of the oxide layer [37] generates
a decrease in CoF at lower sliding distances compared with
the N sample (Fig. 6a and b).
The NP sample showed a higher CoF compared to
the N sample and became stabilized at a sliding distance
of ~ 30 m. In a steady-state sliding, the CoF behavior for the
NP sample is lower compared with the other samples [38].
Mischler et al. [39] established that the system behavior was
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controlled by the formation of a third body, consisting of

2.2753 ± 0.002
0.3997 ± 0.003
0.3469 ± 0.001
separate metallic particles trapped within the contact. While

ΔCW/ΔWC
particle contact is maintained, rupture, corrosion, and trans-
fer are also maintained, and the particles are finally expelled
or trapped from the contact area; thus, the stick–slip phe-
nomena occur, increasing the material removal.

0.7257 ± 0.006
0.4291 ± 0.003
0.5517 ± 0.003
ΔWC/WC
3.4 Corrosion and Wear Results

Parameters of synergetic contributions

0.0612 ± 0.007
0.0278 ± 0.002
0.0228 ± 0.001
Table 3 summarizes the results of tribocorrosion. The corro-
sion rate due to wear (ΔCW) shows a significant increment,
compared to the samples exposed only to C0. The NP sample

C/T
presented a lower wear rate due to corrosion (ΔWC), due to

0.6607 ± 0.004
0.5223 ± 0.003
0.4859 ± 0.002
the contribution of the F­ e3O4 phase. The W
­ 0 in the samples
U and N were high as a result of the layer susceptibility
to corrosion in a 5% NaCl solution, which accelerates the

S/T
volume removal on the surface. Note that, the synergistic
component is related as S = ΔCW + ΔWC and Eq. 3 was taken

1.136 ± 0.002
0.321 ± 0.002
0.212 ± 0.002
into account. However, the total material removal due to cor-
rosion (C) and the total material removal due to wear (W) are

WC
calculated using Eqs. 5 and 6:

0.824 ± 0.003
0.138 ± 0.001
0.117 ± 0.002
C = C0 + ΔCW (5)

ΔWC
W = W0 + ΔWC (6)
In this way, the total material loss (LT) is calculated using

0.562 ± 0.001
0.003 ± 0.001
0.002 ± 0.001
the expression LT = T = C + W. The measure of the effect of
wear on corrosion can be described by the corrosion aug-
ΔCW
mentation factor C/C0, and the effect of corrosion on wear
can be related by the wear augmentation factor W/W0. In 0.768 ± 0.002
0.141 ± 0.005
0.179 ± 0.007
addition, the total synergism factor is represented by T/(T-S).
On the worn tracks, failure mechanisms related with
tribo-chemical products were observed on the surface of the
S

N and NP samples, which accelerated the material removal

0.024 ± 0.001
0.010 ± 0.002
0.004 ± 0.002

[27]. On the counterpart, low adherence was observed,

which indicates the presence of adhesive wear mode. This
behavior is affected by the Hertzian properties on contact
CW

surfaces between tribopairs (U/N/NP/Al2O3 ball), and the

0.048 ± 0.001
0.006 ± 0.001
0.003 ± 0.002

influence of the test parameters.

Galvanic corrosion would occur due to the differences
Table 3  Parameters of synergetic contributions

in potential cathode/anode [2]. The increase in corrosion

C0

speed would be related to material removal/spalling from

the passive film (cathode) [40]. Furthermore, Fig. 7a dis-
Loss material rate (mm × ­year−1)

0.314 ± 0.002
0.153 ± 0.001
0.095 ± 0.001

plays the synergetic contributions of corrosion and the wear

between the total losses of the material of the various con-
W0

ditions in 5% NaCl. The total synergism increase factor is

greater for the condition without thermochemical treatment
0.331 ± 0.015
0.217 ± 0.011
1.171 ± 0.02

(U), while the increase in corrosion-induced wear speed is

far more significant than the corrosion-induced wear speed
itself. Theoretically, the increase in corrosion speed would
T

be linearly related to the damage of the passive film [41].

Sample

Figure 7b and c shows that the degree of contribution of

NP
U
N

13
Journal of Bio- and Tribo-Corrosion (2021) 7:83 Page 9 of 13  83
Fig. 7  (a) Synergistic corrosion contributions, wear, and total material loss, (b) W0, ΔWC, C0, and ΔCW, and (c) Tribocorrosion contribution
after immerse slippage in 5% NaCl
wear-related corrosion is greater than that of corrosion-
related wear. Also, the increase of the speed for ΔCW and
ΔWC is lower for the NP condition; these values are repre-
sented as the synergy (S) contributed to 66%, 52%, and 48%
by S/ L
­ T and 6.1%, 2.7%, and 2.2% by C/ ­LT for U, N, and NP
samples respectively. Thus, the total loss of material is due
to mechanical wear and corrosion during mechanical contact
according to the behavior of the depth in Fig. 5 for both tests.
These results indicate that the synergy between corrosion
and wear represents a significant contribution to the loss of
material, and the loss of material is mainly due to mechani-
cal wear. However, the proportion of accelerated wear due
to corrosion is lower in the NP sample. Not only do corro-
sion and wear co-occur but they are also dependent on one
another, and complex interactions may occur to create an
accelerated loss of material (see Fig. 9).
The worn tracks on the surface samples with W0 (Fig. 8)
and CW (Fig. 9) were analyzed by the SEM–EDS technique.
The specific failure mechanisms were grooving, material
agglomeration, smearing, micro-cracks, and spalling for all
samples, predominating the adhesive, abrasive, and tribo-
oxidative wear modes [42]. Also, for the U samples, plas-
tic deformation/material agglomeration on the edges of the
wear tracks is observed and validated by optical profilometry
[40, 43].
During sliding, wear particles (debris) are detached due
to the interaction of the tribopair (ball and surface), which
generate grooves parallel to the movement. In some cases,
this debris accumulates, producing the material agglomera-
tion and smearing due to the interaction of the NaCl solu-
tion. When the passive film is formed on the surface, cracks
appear in some areas on the wear track product of the tribo-
chemical and chemical reactions, which reduces the material
removal by wear; such adhesive wear appears as spalling;
notice that CoF values fluctuate around ~ 0.35 as observed
in Fig. 6, which involucrate the entrapment and expulsion
of wear particles during sliding.
For the U condition, wear tracks were observed with
grooves and remain, which indicate extensive abrasive wear.
The most expansive worn surface is the U condition for W0
13
 83   Page 10 of 13
Fig. 8  Wear worn tracks surfaces under W0
and CW. The EDS spectra of wear tracks for CW and W0 are
displayed in Fig. 9. The distribution of alloy-related ele-
ments was uniform after testing. On the other hand for all
conditions, the SEM–EDS analysis after T tests a high oxy-
gen content was observed in all wear tracks due to the wear
debris with a high oxygen content being trapped [44]. Notice
also the presence of alloying elements of DIN-16MnCr5 (C,
Si, Mn, Cr, Cu) combined with S and P of the saline solu-
tion and Al of the counterpart. The amount of the O, Cr,
Fe, and Mn decreases with the superficial hardness of the
materials, as observed in Fig. 9 for U-N and NP samples.
When the potential exceeds the exposed metal stinging
potential, the delamination wear is accelerated with the help
of pitting corrosion, which is presented in the N condition.
However, combined with the electrochemical results, was
possible confirm that, when the applied potential is higher
than the metal pitting potential, slippage friction inhibits
corrosion.
13
Journal of Bio- and Tribo-Corrosion (2021) 7:83
A worn track can be observed without the post-oxidation
coating in the substrate due to abrasion. An expanded image
of this track displays a flattening of grains and the forma-
tion of numerous cracks in the coating, an observation that
agrees with previous studies [45]. The EDS spectra obtained
from the wear track (Fig. 9) indicate that the dark areas still
contain the coating material, while lighter areas feature the
substrate. The exposed substrate material is subject to severe
plastic deformation, and to the wear debris formed due to the
breakage of the coating. Also, NP displays the formation of
an oxide film, and severe plastic deformation is visible on
the edge of the wear track.
Journal of Bio- and Tribo-Corrosion (2021) 7:83 Page 11 of 13  83
Fig. 9  Wear worn tracks surfaces under CW
4 Conclusions
The main conclusions about the tribocorrosion behavior
in the DIN-16MnCr5 alloy for the U, N, and NP samples
in saline environments (5% NaCl) obtained in the previous
study are reported as follows:
The presence of a magnetite phase (­ Fe3O4), formed on the
surface of the NP sample from iron nitride by post-oxidizing
treatment, exposed a better tribological performance. This
behavior is attributed to the improvement of the polarization
resistance and the electrochemical corrosion in absence (C0)
and presence of wear (CW), as well as the material removal
(mechanical wear) in the absence of corrosion (W0), com-
pared to the U and N samples. Notice that magnetite phase
increases the superficial hardness around ~ 3.2 times com-
pared to the U sample.
The synergy effect (S) contributes to 66, 52, and 48%
to the total volume removal in the U, N, and NP samples,
respectively. The total material loss of the NP samples
decreased around ~ 5 times related to the U samples. The
presence of a ε-Fe3N phase on N samples aided in the
appearance of the tribocorrosion degradation mechanism.
The wear-corrosion synergy (tribocorrosion—T) contrib-
uted to volume removal in a higher way than wear-corrosion
(∆WC) by themselves than the contribution of corrosion due
to wear (∆CW), with the presence of failure mechanisms as
grooving, smearing, spalling, and material agglomeration
on the wear tracks.
The synergistic effects between wear and corrosion pro-
vide important information about the tribocorrosion phe-
nomenon of DIN-16MnCr5 steels in the N and NP samples
exposed to saline environments (5% NaCl). The presence of
­Fe3O4 provides a potential solution to reduce the degradation
impact in mechanical components for navy military industry
applications, specifically in alarm shutdown systems, lock
pieces, and closer brackets in weapons.
Acknowledgment  The authors acknowledge the support from the
Dirección General de Educación Militar, Mexico.
Author’s contribution  WDW-Á contributed to investigation, methodol-
ogy, formal analysis, and original draft. JM-T was involved in method-
ology, supervision, project administration, formal analysis, and funding
acquisition. IC-S was involved in methodology, supervision, formal
analysis, and other contributions. VH-H and USS-R were involved in
conceptualization, supervision, and other contributions. RAG-L con-
tributed to formal analysis, original draft, writing—review and editing.
Funding  The research Grant 20211111 of the IPN, Mexico.
Declarations 
Competing interest  There are no competing interest to declare.
13
 83   Page 12 of 13 Journal of Bio- and Tribo-Corrosion (2021) 7:83

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