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61a 2021 TRIBO Wear-Corrosion Din-16M
61a 2021 TRIBO Wear-Corrosion Din-16M
https://doi.org/10.1007/s40735-021-00511-w
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).
* 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
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on improving the mechanical and chemical properties of NaCl solution and pin-on-disc configuration. The results
elements used in essential applications (e.g., navy military clearly show an improvement of the corrosion and wear
industry, due to the exposure to saline environments) [1, 2]. performance when the layer thickness increases, and there-
Under corrosive conditions, metallic components are sub- fore, the superficial hardness of the samples is influenced
ject to a friction (wear-corrosion) effect between mechani- by the processing conditions [12, 13]. Hacısalihoglu et al.
cal wear and chemical or electrochemical processes. Wear- [14] studied the effect of plasma nitriding on corrosion,
corrosion synergy, also called tribocorrosion phenomenon, wear, and tribocorrosion behavior on different types of
is present in many mechanical applications. It accelerates steels using a pin-on-disc configuration under NaCl solu-
material damage, compromising equipment security, and tion. The results demonstrated that the nitriding improved
could generate catastrophic failures and economic losses the corrosion and wear resistance and changed the elec-
[3]. During tribocorrosion, the volume removal in materi- trochemical in pitting and peaches failure mechanisms on
als is not a simple sum determined by mechanical wear and the surface [15].
corrosion, but some parameters, such as coatings, mechani- In the case of studies on DIN-16MnCr5, Yegen and
cal contact, environment, and corrosion conditions, should Usta [16] evaluated the effect of salt bath cementation on
also be taken into account [4]. Thermochemical and surface wear resistance and mechanical behavior of DIN-16MnCr5
treatments have been used to reduce corrosion and improve steel. The results showed that the wear resistance of the
the wear rate of metallic components, thus improving the DIN-16MnCr5 steel increases with the cementation pro-
useful life of the materials [5]. cess due to the improvement of the superficial hardness,
Studies related to the tribocorrosion tests have measured which increases with the exposure time. In the same way,
additional corrosion due to wear by applying the ASTM Brodyanski et al. [17] studied the microstructural and
G119-09 standard methodology to examine wear-corro- chemical changes during the application of load on the
sion synergy [6]. The synergistic effect between the loss of DIN-16MnCr5 steel case hardened by various laboratory
mechanical wear and electrochemical corrosion in materials methods. The results indicate that the thermal treatment
can be described as S = T–W0–C0, where the synergy factor improved the superficial hardness around 3.5 times, simi-
(S) between corrosion and wear is determined by the total lar to Ref. [18]. Due to the superficial treatment, a trans-
loss of material in the medium (T) minus the rate of lost formation phase is provoked from γ-austenite to ε- and
material due to wear with cathodic protection (W0) and the α′-martensite, with the appearance of an oxidative layer
corrosion rate without wear (C0) [7]. on the surface. Also, the authors demonstrate that during
On the other hand, Zhang et al. [8] studied the behavior sliding high residuals stresses appear (~ 10 GPa), which
of the AISI 1045 steel and AISI 2205 duplex stainless steel was manifested in sub-surface elastic strains. Wong-Ángel
under pin-on-disc configuration to elucidating the degrada- et al. [2] performed a tribocorrosion test on the carburized
tion due to tribocorrosion under corrosive environments. samples of DIN-16MnCr5 immersed in a saline solution
The results showed that the interplay between chemical, under different test parameters. The results showed that the
mechanical, and electrochemical processes aids both corro- carburized sample plus manganese coating increased the
sion and corrosion due to wear, in consequence, significant tribocorrosion effect around 3.8 times due to the increase
degradation of the material without coating. Also, high val- of the superficial hardness.
ues of CoF and the destruction of the passive layer increased Ceiari and Timelli [19] optimized the oxy-nitro-car-
material removal by wear. Eghlimi et al. [9] investigated burizing process on the DIN-16MnCr5 steel for industrial
the tribocorrosion behavior of a super duplex stainless steel components by reducing the processes. The results showed
under pin-on-disc configuration in NaCl solution. The results that it is possible to increase the magnetite layer thickness
demonstrated a significant effect of the applied potential on on the compound zone, increasing the temperature and
the wear and corrosion synergy. Therefore, degradation and time of exposure under the N2O atmosphere, providing
material removal involve sequential wear and wear due to improved wear and corrosion results.
corrosion. El-Aziz et al. [10] evaluated the tribocorrosion In this work, new results about the wear-corrosion syn-
behavior of the Al-Si alloy reinforced with A l2O3 particles ergy on DIN-16MnCr5 steel were obtained on three dif-
on samples immersed in NaCl solution under pin-on-disc ferent samples under ball-on-flat configuration: untreated
configuration. The results revealed that a significant concen- (U), nitriding (N), and nitriding plus post-oxidation pro-
tration of A
l2O3 particles improves the corrosion resistance cess (NP) immersed in a NaCl solution to evaluate the
influenced by the speed and wear values. mechanical–chemical behavior under marine saline condi-
Tribocorrosion studies on nitride and post-oxidation tions for navy military industry applications, specifically
process materials are few. Fernandes et al. [11] reported in alarm shutdown system, lock piece, and closer bracket
the influence of the nitride and nitride plus oxidation on in weapons, which have not been reported in the open
the tribocorrosion properties on a Ti6Al4V alloy under literature.
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Nitriding is a thermochemical treatment that provides Nitro- CO2 + NaCN → NaCNO + CO. (1.4)
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- 2.1.2 Nitriding Plus Post‑Oxidizing Process (NP)
ried out in a crucible container and consists of a liquid solu-
tion with cyanide salts. The most common components used The post-oxidation process consists mainly of six steps: (1)
for thermochemical treatment is 60–70 wt% sodium cyanide degreasing, (2) preheating, (3) nitriding, (4) oxidant, (5)
(NaCN) and 30–40 wt% potassium cyanide (KCN). This washing, and finally (6) oil immersion [25]. The samples
process requires preheating the component to be nitrided to must be previously preheated to a temperature of around
420 °C and then entering it into a molten salt bath at 580 °C 380 °C as usual in salt bath treatments. In this way, nitriding
for a period that depends directly on the composition of the is generally carried out between 30 and 120 min at 580 °C
material and the layer thickness required to be obtained. In (TF1 salt bath). Subsequently, the samples are introduced
this way, the (N) treatment was performed at 580 °C for 6 h into the oxidizing bath (Salt Bath AB1) at a temperature of
according to the considerations reported by Funatani [24]. 420 °C for 20 to 30 min; finally, the samples are placed in an
The nitrogen diffusion on the surface of the ferrous mate- oil wash bath. Note that if after nitriding the surface of the
rial generates a compound zone following a diffusion zone parts is too rough, mechanical polishing can be applied; this
that consists of an iron matrix with nitrites precipitated that process has been widely described in the literature [26, 27].
react with the alloying elements. This phase depends on the In the post-oxidizing process, some (N) samples were
treatment conditions and the efficacy of the nitriding agent. exposed to an (NP) process with post-oxidation in a
During this process, when the sample is immersed in the 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].
Table 1 Relevant mechanical–physical properties of DIN-16MnCr5
steel
2.2 Corrosion‑Wear Synergy Tests
Property Value
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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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
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3 Results and Discussions resistance in a better way [33, 34]. Notice that, from Table 1,
the mechanical–physical properties of the DIN-16MnCr5
3.1 Microstructure and Mechanical Properties can be improved with the use of different thermal treatments
of the N and NP Samples and methods of cooling that increase the superficial hard-
ness (2, 3, even four times more), and therefore the wear
Figure 2a and b shows a layer thickness of ~ 25 and ~ 22 μm and corrosive protection under different environments and
with a surface hardness of 6.04 and 6.68 GPa for N and test conditions.
NP, respectively. Figure 2c shows the XRD pattern for the
treated samples revealed the presence of F e3O4, ε-Fe3N, 3.2 Electrochemical Corrosion
and a compound layer, indicating that the surface layer is
mainly composed of ε-Fe3N, which provides a higher hard- The corrosion current density values (I corr) were deter-
ness and excellent wear resistance [32]. The main differ- mined with Tafel extrapolation (potentiodynamic polariza-
ence between the two treatments N and NP is the forma- tion curves) using Eq. 2, considering also a linear region
tion of Fe3O4 phase, thus improving the corrosion and wear 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
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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
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in the test without wear (C0). However, when the load is the material removal through mechanical contact and repas-
applied over the surface, the corrosion current density sivation of the passive layer; in the final tests the OCP values
increases by a factor of 101–102 [35]. reached negative values.
The results of volume removal during the W0 test were
3.3 Friction and Wear Behavior calculated via optical profilometry, obtaining depths of
around 30, 14, and 3 µm for U, N, and UP, respectively,
Volume removal in mechanical components is due to differ- as it is shown in Fig. 5a and b. These values are directly
ent mechanisms of W0 and CW [36]. From Fig. 4, the poten- influenced by the superficial hardness obtained through the
tial in the medium was measured to determine behavior, thermochemical processes of nitriding and nitriding plus
observing a drop (zone 1) in the chart shown in Fig. 5 due post-oxidizing.
to the removal of de-passivation films formed in the samples. The corrosion products developed on the worn tracks can
In zone 2, the active metal footprint left by the action of the change the CoF and W0. In the case of the W0 test, CoF was
alumina ball over the sample is more prone to accelerated between 0.35 and 0.40, but in the case of the CW, a low
corrosion due to wear. In zone 3, the alumina ball ceased to value was obtained between 0.25 and 0.42. For W0 on NP
act over the surface, and the passive film was formed again. samples, the lower adhesion of the oxide layer [37] generates
The second mechanism is due to the metal particles detached a decrease in CoF at lower sliding distances compared with
due to the action of the shank with the Al2O3 alumina ball on the N sample (Fig. 6a and b).
the metal surface. Note that OCP showed a decrease for the The NP sample showed a higher CoF compared to
three samples in zone 1; thus, the U sample released nega- the N sample and became stabilized at a sliding distance
tive values (~ 350 V) when the test started. In the opposite of ~ 30 m. In a steady-state sliding, the CoF behavior for the
case, the N and UP shown positive values of around ~ 150 V. NP sample is lower compared with the other samples [38].
During the tests (Zone 2), OCP values are constant due to Mischler et al. [39] established that the system behavior was
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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
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
0.314 ± 0.002
0.153 ± 0.001
0.095 ± 0.001
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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- samples, predominating the adhesive, abrasive, and tribo-
related wear. Also, the increase of the speed for ΔCW and oxidative wear modes [42]. Also, for the U samples, plas-
ΔWC is lower for the NP condition; these values are repre- tic deformation/material agglomeration on the edges of the
sented as the synergy (S) contributed to 66%, 52%, and 48% wear tracks is observed and validated by optical profilometry
by S/ L
T and 6.1%, 2.7%, and 2.2% by C/ LT for U, N, and NP [40, 43].
samples respectively. Thus, the total loss of material is due During sliding, wear particles (debris) are detached due
to mechanical wear and corrosion during mechanical contact to the interaction of the tribopair (ball and surface), which
according to the behavior of the depth in Fig. 5 for both tests. generate grooves parallel to the movement. In some cases,
These results indicate that the synergy between corrosion this debris accumulates, producing the material agglomera-
and wear represents a significant contribution to the loss of tion and smearing due to the interaction of the NaCl solu-
material, and the loss of material is mainly due to mechani- tion. When the passive film is formed on the surface, cracks
cal wear. However, the proportion of accelerated wear due appear in some areas on the wear track product of the tribo-
to corrosion is lower in the NP sample. Not only do corro- chemical and chemical reactions, which reduces the material
sion and wear co-occur but they are also dependent on one removal by wear; such adhesive wear appears as spalling;
another, and complex interactions may occur to create an notice that CoF values fluctuate around ~ 0.35 as observed
accelerated loss of material (see Fig. 9). in Fig. 6, which involucrate the entrapment and expulsion
The worn tracks on the surface samples with W0 (Fig. 8) of wear particles during sliding.
and CW (Fig. 9) were analyzed by the SEM–EDS technique. For the U condition, wear tracks were observed with
The specific failure mechanisms were grooving, material grooves and remain, which indicate extensive abrasive wear.
agglomeration, smearing, micro-cracks, and spalling for all The most expansive worn surface is the U condition for W0
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and CW. The EDS spectra of wear tracks for CW and W0 are A worn track can be observed without the post-oxidation
displayed in Fig. 9. The distribution of alloy-related ele- coating in the substrate due to abrasion. An expanded image
ments was uniform after testing. On the other hand for all of this track displays a flattening of grains and the forma-
conditions, the SEM–EDS analysis after T tests a high oxy- tion of numerous cracks in the coating, an observation that
gen content was observed in all wear tracks due to the wear agrees with previous studies [45]. The EDS spectra obtained
debris with a high oxygen content being trapped [44]. Notice from the wear track (Fig. 9) indicate that the dark areas still
also the presence of alloying elements of DIN-16MnCr5 (C, contain the coating material, while lighter areas feature the
Si, Mn, Cr, Cu) combined with S and P of the saline solu- substrate. The exposed substrate material is subject to severe
tion and Al of the counterpart. The amount of the O, Cr, plastic deformation, and to the wear debris formed due to the
Fe, and Mn decreases with the superficial hardness of the breakage of the coating. Also, NP displays the formation of
materials, as observed in Fig. 9 for U-N and NP samples. an oxide film, and severe plastic deformation is visible on
When the potential exceeds the exposed metal stinging the edge of the wear track.
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.
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