Surfaces and Interfaces 36 (2023) 102352

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Surfaces and Interfaces

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Study of the influence of a gradient gas flow as an alternative to improve

the adhesion of Diamond-Like Carbon film in the wear and corrosion
resistance on the nitrided AISI 4340 steel
Miguel Rubira Danelon a, *, Larissa Solano de Almeida a, Marcos Dorigão Manfrinato a, b, Luciana
Sgarbi Rossino a, b
a
Postgraduate Program in Materials Science (PPGCM), Federal University of São Carlos, UFSCar Sorocaba Campus, Rodovia João Leme dos Santos, Km 110, Bairro do
Itinga, Sorocaba, SP 1805780, Brazil
b
Sorocaba Technological College (FATEC Sorocaba), CEETEPS, Avenida Engenheiro Carlos Reinaldo Mendes, Alto da Boa Vista, Sorocaba, SP 18013280, Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Diamond-Like Carbon (DLC) films have been widely studied due to their interesting properties, but this film
Gradient gas flow presents low adhesion on metal surfaces. Interlayers have been performed, between the substrate and the DLC
Adhesion film, combined with previous surface treatment as plasma nitriding to improve film adhesion on the surface. This
Micro-abrasive wear
work aims to develop a multilayer treatment of nitriding, gradient treatment, and DLC film deposition without
Corrosion potential
organosilicon interlayer to determine the synergic influence of treatments on multilayer adhesion, wear, and
corrosion resistance of the AISI 4340 steel. Plasma surface treatments such as simple nitriding, simple DLC film
deposition, which consists of treatments performed individually, multilayer treatment of nitriding + DLC with
and without an organosilicon interlayer, and multilayer treatment of nitriding + gradient treatment + DLC
without interlayer using gas flow gradient were carried out using a pulsed-DC power supply. The highest wear
and corrosion resistance was obtained by the multilayer treatment with organosilicon interlayer due to the
synergic effect of this interlayer with the DLC film and nitriding treatment, but the multilayer treatment without
organosilicon interlayer performed with gas flow gradient presents better corrosion and wear properties
compared with simple treatment. Results have shown that it is possible to perform multilayer treatments with the
presence and the absence of an organosilicon interlayer, keeping wear, corrosion, and adhesion properties of the
DLC film on nitrided AISI 4340 steel deposition.

1. Introduction
AISI 4340 steel is a structural metal that presents high mechanical
resistance, normally used tempered and quenched, allowing it to be used
in a wide range of applications, in situations where high resistance to
great mechanical efforts is required, like structural components for
space vehicles, and landing gears for aircraft [1–3]. Some situations
which require high wear resistance may compromise the steel behavior,
like when used in milling tools. In this situation, the component can be
worn quickly, and this problem can be solved with surface treatments
[4].
Plasma surface treatments are explored as new technology sources,
used to obtain materials with excellence and improve their tribological,
corrosion, and fatigue properties. For example, the Diamond-Like
Carbon (DLC) films deposited by plasma have properties like chemical
inertia, high hardness, interesting optical properties, and low friction
coefficient, and can be used as a solid lubricant [5,6]. Thermochemical
treatments are the ones where the diffusion of different elements is the
main objective. These elements need to have a small atomic radius to
provide their interaction with the base material, causing superficial
changes on the surface of the treated material without microstructural
changes in the core. Plasma nitriding is one of the most used thermo­
chemical treatments, in which the wear resistance, corrosion, and fa­
tigue properties are improved, due to a nitride layer, with ceramic
characteristics formed on the surface of the metal and the diffusion zone
formed just below the compound layer [7–10].
Surface modifications by plasma treatments can provide special
properties of the metals as multilayer treatments, which are used when

* Corresponding author.
E-mail address: miguel.danelon@estudante.ufscar.br (M.R. Danelon).

https://doi.org/10.1016/j.surfin.2022.102352
Received 26 May 2022; Received in revised form 6 August 2022; Accepted 15 September 2022
Available online 23 September 2022
2468-0230/© 2022 Published by Elsevier B.V.
M.R. Danelon et al.
one or more treatments are performed in a specific order, so it is possible
to apply the individual properties of each treatment during work [11,
12]. However, good interaction between the treatments must be ob­
tained to ensure the desired superficial properties, for example, it is
essential for the DLC to have good adhesion on the nitrided surface, so
both layers can act synergistically and provide greater resistance for the
materials [13,14].
For example, in the duplex treatments, the DLC films determine the
material wear resistance, while the nitriding treatment guarantees the
fatigue and corrosion resistance of the treated metals. However, for this
proper interaction to occur, the DLC film must have adequate adhesion
to the nitrided metallic substrate [12].
To ensure adequate adhesion of the DLC films on the nitrided or
nitrocarburized metallic substrates, some techniques have been used
such as deposition of thin film as an interlayer of silicon or organosilicon
[11], chromium nitride [15] or tungsten carbides [16], which vary ac­
cording to the substrate affinity with the deposited film. Other tech­
niques can be used, such as the DLC film doping with elements like
nitrogen and silicon [17].
The main objective of this work is to develop a multilayer treatment
without the deposition of a thin film as an interlayer and guarantee
adequate adhesion of the DLC film to the metallic substrate, evaluating
the synergy between those treatments in wear and corrosion resistance
of the AISI 4340 steel. It has been studied a performance comparison
between the simple treatments and the multilayer treatments in the
tribological properties and corrosion resistance of the studied material.
Thus, a range of treatments, varying gas mixtures, presence and absence
of compound layers and interlayers between compound layer and DLC
film, good and bad adhesion of DLC film on the substrate, and different
interlayers have been studied, and its wear and corrosion behavior were
evaluated, to show the properties of each treatment, separately and
jointly, applied on AISI 4340 steel.
2. Materials and methods
The material used for this study was AISI 4340 steel (0.43 wt%, 0.8
wt%, 1.79 wt%, 0.2 wt%, 0.79 wt% of Mn, and Fe bal.) due to its wide
applicability in the mechanical industry. Samples with a diameter of
25.4 mm and a thickness of 10 mm were sanded, polished, and cleaned
with detergent and alcohol in an ultrasound machine. After cleaning and
drying, the samples were superficially treated. Plasma surface treat­
ments were performed at LabTES (Surface Treatment and Engineering
Laboratory). The treatment system is shown in Fig. 1, presenting the
schematic view of the characterization methods and scheme of the
performed treatments.
The plasma treatment was initiated with a plasma ablation cleaning
Fig. 1. Treatment system and schematic view flowchart of characterization methods and performed treatments.
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Surfaces and Interfaces 36 (2023) 102352
carried out with 80% Ar + 20% H2, for 1 h and 2 torr, at a temperature of
respective treatment. Immediately, the surfaces treatments were carried
out, in which the parameters of the simple treatments (nitriding and
DLC) are presented in Table 1, and the parameters of the multilayer
treatments (nitriding + DLC) with the presence and absence of orga­
nosilicon interlayer are presented in Table 2, and the parameters of the
multilayer treatments with gas flow gradient (nitriding + grad + DLC)
without the organosilicon interlayer are shown in Table 3. The vacuum
range of the plasma nitriding was between 2.4 and 15.1 torr and for the
DLC, film the pressure during treatment was 0.3 torr.
Microhardness tests were performed according to ASTM E348-99
standard with an application time of 15 s in a Mitutoyo HM220 digital
microhardness tester on treated and untreated samples to determine the
surface hardness with a load of 0.1 kgf. To determine the hardness
profile of the total formed layer, a load of 0.01 kgf was used. The
penetration depth was varied according to the diffusion zone depth of
nitrided samples, where the highest penetration depth was 0,45 mm.
The measurements were made until 3 similar values of hardness were
found.
Metallographic analyzes were performed on the treated and un­
treated samples from the cross-section of the substrate, which were
embedded with high adhesion Bakelite. The samples were also ground in
water sandpaper with granulometry from #220 to #2500, polished with
3μm diamond paste, and chemically etched with Nital 3% (97% Ethyl
Alcohol – 3% Nitric Acid). EDS (Energy Dispersive Spectroscopy) ana­
lyzes were also made, to identify the semi-quantitative chemical ele­
ments in the layer formed by the treatments using a Hitachi TM-3000
benchtop Scanning Electron Microscope (SEM) with 15 kV.
To identify the formed compound layers on the surface of the ma­
terials, X-Ray Diffraction (XRD) analyzes were performed in a contin­
uous mode using Cu-Kα radiation with an incidence angle of 5◦ . The
equipment utilized was an XRD Bruker D8 Advance.
For the DLC film characterization, Raman Spectroscopy was per­
formed, with an argon laser at a wavelength of 514 nm, 5% of the total
power of the equipment, and a laser spot diameter of 5 μm. The equip­
ment used was a Renishaw Via Raman Microscope, and the obtained
specters were analyzed by the software Fityk 0.9.8. The percentage of
hydrogen contained in the film was determined by Eq. (1) [18].
H [at.%] = 21.7 + 16.6 log (m / I(G)[μm] (1)
where I(G) is the G peak intensity and m is the slope of the spectrum
between 1000 and 1800 cm− 1.
DLC film adhesion tests were performed according to VDI 3198
standard [19]. Rockwell C hardness tests were performed in a hardness
tester Mitutoyo - HR 300, and the images of the obtained indentations
were acquired by a Hitachi TM-3000 SEM and analyzed by ImageJ
M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Table 1
Parameters of the simple treatments.
Nomenclature Treatment Gas Mixture (%) Temperature (◦ C) Gas Flow Time (h)

DLC Organosilicon Interlayer Deposition 70 HMDSO + 30 Ar 300 0.042 torr HMDSO + 0.018 torr Ar 0.25
DLC Deposition 90 CH4 + 10 Ar 200 30 sccm 2
NIT80 Nitriding 80 N2 + 20 H2 450 500 sccm 5
NIT05 05 N2 + 95 H2

Table 2
Parameters of the multilayer treatments.
Nomenclature Treatment Gas Mixture (%) Temperature (◦ C) Gas Flow Time (h)

NIT80+DLCw Nitriding 80 N2 + 20H2 450 500 sccm 5

Organosilicon Interlayer Deposition 70 HMDSO + 30 Ar 300 0.042 torr HMDSO + 0.018 torr Ar 0.25
DLC Deposition 90 CH4 + 10 Ar 200 30 sccm 2
NIT05+DLCw Nitriding 05 N2 + 95 H2 450 500 sccm 5
Organosilicon Interlayer Deposition 70 HMDSO + 30 Ar 300 0.042 torr HMDSO + 0.018 torr Ar 0.25
DLC Deposition 90 CH4 + 10 Ar 200 30 sccm 2
NIT80+DLCw/o Nitriding 80 N2 + 20 H2 450 500 sccm 5
DLC Deposition 90 CH4 + 10 Ar 200 30 sccm 2
NIT05+DLCw/o Nitriding 05 N2 + 95 H2 450 500 sccm 5
DLC Deposition 90 CH4 + 10 Ar 200 30 sccm 2

3. Results and discussion

Table 3
Parameters of the multilayer treatments with gas flow gradient.
3.1. Simple treatments
Nomenclature Treatment Gas proportion/time Gas
Flow
Fig. 2(a) presents the metallography of the layer formed in the NIT80
NIT80+ GRAD + Nitriding 0 h to 1 h – 80N2-20H2 500 treatment. It is possible to observe the compound layer formation,
DLC 1 h to 2 h – 65N2-35H2 sccm
indicated by the red line, with a thickness of 3.6 µm, in which its for­
2 h to 3 h – 50N2-50H2*
3 h to 4 h – 35N2-65H2
mation is justified by the high potential of nitrogen during treatment [8]
4 h to 5 h – 20N2-80H2 favoring the formation of the iron nitrides. On the other hand, it was not
Gradient 5CH4-75N2-20H2 500 possible to observe the formation of the compound layer in the NIT05
treatment sccm sample, and this is explained by the low nitrogen potential during this
DLC Film 0 h to 0.5 h – 10CH4- 30 sccm
condition of treatment. However, it is possible to confirm that the per­
90Ar
0.5 h to 1 h – 35CH4- formed treatment was effective in the nitrogen interaction with the base
65Ar metal, proved by the nitrogen diffusion in the substrate observed in the
1 h to 1.5 h – 60CH4- EDS analysis, presented in Table 4.
40Ar It is observed that sample NIT05 had a lower amount of nitrogen
1.5 h to 2 h – 90CH4-
10Ar
when compared with the same region of sample NIT80. It is also
explained by the lower nitrogen potential existent in the NIT05 treat­
*The hydrogen gas flow was not changed, only the nitrogen gas flow. ment, providing less diffusion of this element in the substrate [8].
Fig. 2(b) shows the formation of a uniform DLC film, with a 2.35 µm
software, to determine the adhesion area of the film. thickness, indicated by the black line. The formation of the film was
Micro-abrasive wear tests by fixed ball were performed on all treated confirmed by the presence of carbon found in EDS analysis. The presence
and untreated samples, with a test load of 8 N, a rotation frequency of of silicon also determined by the EDS analysis is explained by the
158 RPM, and a test time of 600 s (10 min). Wear volume (V) was deposition of the organosilicon film, between the DLC film and the
determined by Eq. (2) to determine the wear resistance of the studied substrate. The formation of the organosilicon layer is confirmed in de
materials, where R is the sphere radius and b is the crater diameter Campos et al. [12], whose deposition parameters and studied material
obtained during the test [20]. Tests were performed in a duplicate and are the same as those utilized in this work.
without any kind of abrasive liquid or lubricant. Measures of the crater Nitrogen diffusion can also be observed in Fig. 3, where is presented
were performed on a Leica DMi8 C optical microscope, with an image the metallography taken by an optical microscope. It is possible to note
capture camera MC170 HD. the presence of both the compound layer (white layer), identified by a
/ ( / ) / red line and the beginning of the diffusion zone identified by a blue line.
V = π b4 64R2 R − b2 8R ≈ πb4 64R to b <<< R (2)
The beginning of the diffusion zone is characterized by a darker region
Corrosion tests were performed on treated and untreated samples by below the compound layer. The complete diffusion zone is only char­
the potentiodynamic polarization (PP) test at a Gamry Ref 600 poten­ acterizable by microhardness tests because there is the presence of a
tiostat/galvanostat, with a platinum counter electrode (CE) and an Ag/ supersaturated solution of nitrogen in the iron even after the “darker
AgCl/KClsat reference electrode. Curves were obtained from the test region” no longer appears in the metallography.
with a sodium chloride solution (3.5% w/w NaCl) with an exposed area For the DLC film characterization, the Raman spectroscopy is pre­
of the samples of 0.8 cm2 at room temperature (25 ± 1 ◦ C) in triplicate sented in Fig. 4. G peak, which represents carbon sp2 hybridizations and
by using a scan rate of 1 mV s− 1. graphite presence in the film, was found at 1539.3 cm− 1 and the D peak,
which represents the angular changes of carbon bonds and diamond
aspects in the film due to the presence of C-C sp3 hybridizations, was
found at 1357.23 cm− 1. Such results corroborate with results found in
the literature [21]. Also according to the literature [18,21], it can be

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M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Fig. 2. Sample metallography (A) NIT80, (B) DLC, (C) NIT05+DLCw, (D) NIT80+DLCw, (E) NIT80+DLCw/o, and (F) NIT80+GRAD+DLC.

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M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Table 4 samples.
Point EDS analysis of the N and Fe elements present in nitride layers. Carbon is present in the NIT80+GRAD+DLC sample due to the
Point Position Treatment gradient treatment performed before the nitriding and before the DLC
NIT80 NIT05 film deposition. However, it was not expected that carbon was present in
Atomic Percentage (% at) Fe – N Fe – N the NIT80+DLC sample since the only treatment with carbon was the
Point 1 82.92 – 17.08 94.92 – 5.08 DLC film and due to its amorphous characteristic, the XRD analysis
Point 2 89.18 – 10.82 96.12 – 3.88 would not detect it. The authors hypothesize that since Fe has an affinity
Point 3 92.14 – 7.86 99.73 – 0.27 with C, due to its electron configuration which there are few vacancies in
orbital d [23], the carbon of the DLC film is merging into the compound
layer, bonding with Fe and N, transforming ε nitride in ε’ carbonitride.
It is also important to observe that the carbon promotes the forma­
tion of ε nitride When comparing samples with the presence of carbon,
for instance, samples NIT80+DLCw and NIT80+GRAD+DLC, with
samples without the presence of carbon, for example, sample NIT80, it is
possible to observe that the ε nitride peak is easier to identify when the
carbon is present. This is explained by the combination of the carbon
from the gradient layer after the nitriding treatment with the carbon
which probably came from the DLC film deposition. These results
corroborate with Sun and Bell [7], which says that carbon contributes to
the stabilization and formation of ε nitride, due to its high solubilization
of carbon in the nitride.
Table 5 presents the hardness and thickness results of the compound
layer and diffusion layer, and the microhardness profile of the simple
treatments is presented in Fig. 6(a). The NIT80 sample has shown a
superficial hardness of 662HV while the sample NIT05 presented a
hardness of 317HV. This difference is explained by the presence of a
hard and ceramic compound layer formed in the NIT80 treatment [24].
The NIT05 condition has not presented a compound layer formation and
showed a lower superficial hardness when compared to the NIT80
Fig. 3. Metallography of sample NIT80+DLCw taken by optical microscope treatments. However, the hardness is higher than the substrate (170HV)
with magnification of 100x. due to the nitrogen diffusion in the substrate.
It is observed that the sample NIT80 has shown a higher hardness in-
depth when compared to sample NIT05, which confirms the formation
of a thicker diffusion zone, due to the higher nitrogen diffusion provided
in this treatment condition, as shown in Table 4, which corroborates
with the result presented by Lopes et al. [25].
DLC film presented a superficial hardness of 1188HV, while the
substrate obtained a 170HV hardness. This occurs as a result of the
presence of sp3 carbon hybridizations, which are similar to the diamond
structure so that they increase the hardness of the material [26].
Fig. 7(a) shows the wear volume obtained for the simple treatments.
It can be noted that treated materials presented lower wear volume
compared to the base metal, evidencing the effectiveness of the super­
ficial treatments. The NIT80 sample presented greater wear resistance
than the NIT05 and this is justified by the compound layer formed in the
NIT80 sample, which increases the superficial hardness of the material.
Furthermore, the higher in-depth hardness of sample NIT80 ensures a
better wear performance. These results agree with the ones found by
Danelon et al. [27] and Lopes et al. [25].
DLC film showed a higher wear resistance when compared to base
material and NIT05, and this is justified by the high hardness and lower
coefficient of friction of the DLC film [28]. However, although the DLC
film presented a higher superficial hardness, the parameters such as the
thicker layer, and the greater depth hardness obtained in the NIT80
Fig. 4. Raman spectroscopy obtained by the DLC film deposited on the sample were more effective in the wear behavior than the other simple
4340 steel. treatments, corroborating with [13].
Analysis of the craters, presented in Fig. 8, has shown that the wear
affirmed that the produced film is defined as an a-C: H hard film, with a mode found in samples with a wear volume above 5,0 × 10− 3 mm3 is
hydrogen quantity of 34.29% and I(D)/I(G) of 0.33. These results were grooving, characterized by the vertical scars in the crater, shown in
also found by Almeida et al. [22]. Fig. 8(a). According to Mergler and Huisin‘t Veld [29], the grooving
X-Ray Diffraction analysis is presented in Fig. 5. Sample NIT80 has wear mode occur during tests with a high load and a low presence of
presented γ’ (Fe4N) and ε (Fe2-3N) nitrides. Samples NIT80+DLCw and abrasive liquid, which corroborates with this work since the samples
NIT80+GRAD+DLC have shown the presence of ε nitride and γ’ and the whose wear mode were grooving, did not present a compound layer, so
presence of ε’ (Fe2-3(C, N)) carbonitride. The ε’ carbonitride is found the debris coming off the layer did not act like an abrasive. However,
when there is the presence of carbon and nitrogen bonding with iron, when analyzing Fig. 8(b), the nitrided sample which has presented wear
and this happens both in NIT80+DLCw and NIT80+GRAD+DLC volume below 5,0 × 10− 3 mm3, it is possible to observe the presence of a

5
M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Fig. 5. XRD analysis of samples BM, NIT80, NIT80+DLC and NIT80+GRAD+DLC.

Table 5
Surface hardness and thickness of the layers formed in the simple treatments.
Treatment Condition Hardness (HV) Thickness (μm)
DLC Compound Layer Diffusion Zone DLC Compound Layer Diffusion Zone Total

DLC 1188 - - 2.35 - - 2,35

NIT05 - - 317-170 - - 200.00 200
NIT80 - 662 290-170 - 3.63 416.37 420
NIT05+DLCw 1198 - 224-170 2.14 - 317.86 320
NIT80+DLCw 1178 413 305-170 2.62 2.68 394.70 400
NIT05+DLCw/o - - 294-170 0.62 - 219.38 220
NIT80+DLCw/o - 648 348-170 - 3.91 336.10 340
NIT80+GRAD+DLC 1021 384 293-170 2.32 6.62 250.60 340

Fig. 6. Microhardness profile results of (A) nitrided samples and (B) multilayer treatments.

6
M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Fig. 7. Wear tests of samples comparing the base material with (A) simple treatments and (B) multilayer treatments.

Fig. 8. Crater obtained by micro-abrasive wear test by fixed ball on sample (a) NIT05, (b) NIT80, and (c) NIT80 + DLCw.

mixed wear mode (grooving + rolling). The rolling wear mode generally
occurs when there is an abrasive liquid during the test. On the contrary
to the samples which have shown grooving wear mode only, the nitrided
sample has a compound layer on its surface, which act like an abrasive
during the test because particles come off the compound and roll in the
wear region [29,30].
In addition, Kusano and Hutchings [31] studied that the rolling wear
mode presents a lower magnitude of the coefficient of friction when
compared to the grooving wear mode, corroborating with the results
found in this work, which has shown that samples with a wear volume
above 5,0 × 10− 3 mm3 presented grooving wear mode, while samples
which have presented a mixed wear mode, presented lower wear
volumes.
Fig. 9(a) shows the corrosion results for untreated and simple treated
samples. It is possible to observe that NIT80 and DLC treatments pre­
sented higher corrosion resistance when compared to the base material
and NIT05 treatment. The NIT80 sample presented the highest corrosion
potential (Ecorr) among all simple treatments, with a value of -0.413 V.

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M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Fig. 9. Corrosion results of the material with (A) simple treatments, and (B) multilayer treatments.

The DLC film presented a corrosion density (icorr) of 6.716 × 10− 8 A/
cm2, indicating a lower corrosion rate when compared to the other
simple treatments. These values are justified by the presence of a
ceramic compound layer existent in the NIT80 sample, which makes the
ions exchange between the material and solution difficult, improving
the corrosion resistance of the sample treated in this condition [32],
while the DLC film presents chemical inertia characteristics, whose
behavior is complemented by the organosilicon interlayer [12,14].
The NIT05 sample showed a different corrosion behavior among
other samples, where treated material showed lower corrosion
resistance when compared to the base material, with an Ecorr of -0.684 V
for base material and -0.845 V for the NIT05 sample. This fact is justified
by the formation of fine nitrogen precipitates, shown in Fig. 10, which
may have provided the formation of galvanic cells, which accelerate the
corrosion process on the surface of the material, as evidenced in the
pitting zone, corroborating with the result found by Liu, et al., where a
galvanic couple generated by a precipitate increases the corrosion rate
of the sample [33].
Pitting in a corrosion process is characterized by a rapid and sudden
increase in current density, and occurs when the surface layer that

Fig. 10. Precipitate located in the pitting region.

8
M.R. Danelon et al.
protects the material breaks or when the solution comes into contact
with the substrate through defects in the layer [34]. Due to the presence
of a compound layer with high corrosion resistance, the NIT80 sample
showed the highest pitting potential (Epit) among the simple treatment
samples, with -0.755 V. DLC film also has shown this behavior,
although, demanding a lower amount of energy to start the pitting for­
mation, with an Epit of -0.480 V. The high Epit indicates the good
corrosion resistance of the film, once it requires more energy to start the
pitting formation and less susceptibility to corrosion. It is possible to
observe that the NIT05 sample presented Epit like Ecorr, denoting a direct
corrosion process, without the pitting formation step. This is justified by
the absence the formation of a corrosion resistance layer on the material
surface.
Fig. 11 shows the topography of the surface sample after the corro­
sion test. It is possible to observe that the untreated sample, NIT05, and
DLC presented larger pits and in greater quantity than pits found in the
NIT80 sample, proving the low tendency to corrosion of the NIT80
sample. It is important to observe that, according to de Campos et al.
[12], the protective layer forces the corrosive environment to find de­
fects such as cracks in the layer so that it can start the formation of pits.
When there is no compound layer, the corrosion fluid acts directly on the
metal and corrodes the entire tested surface. This behavior can be seen
in the base material and the NIT05 sample.
According to VDI 3198 standard, it is possible to define that the film
adhesion of simple DLC on the substrate is acceptable, classified as HF4,
as presented in Fig. 12. This result is explained by the presence of the
silicon interlayer between the substrate and the film, reducing tensions
between them and improving the adhesion of the film on the metal
surface. This result was also found by Cemin et al. [35].
3.2. Multilayer treatments
Fig. 2(c) presents the micrography of the layer formed in the sample
NIT05+DLCw, in which it is possible to observe the presence of the DLC
film with 2.40 µm thickness, indicated by the black line, and the orga­
nosilicon interlayer indicated by the yellow line, evidenced by the EDS
analysis. Micrography of the layer formed NIT80+DLCw is presented in
Fig. 2(d), and it is possible to observe a DLC film with a thickness of 2.62
µm pointed by a black line and a compound layer with a thickness of
3.91 µm, indicated by the red line. These samples showed good adhesion
of the DLC film on the substrate due to the presence of the organosilicon
interlayer, which reduces residual stresses and thermal expansion be­
tween the film and metallic substrate [35].
In Fig. 2(e), which shows the metallography of the sample
NIT80+DLCw/o, it is possible to observe the existence of the compound
layer without the DLC film due to its delamination even with the pres­
ence of a nitriding treatment performed previously [36]. This result
evidences the necessity of an interface between the substrate and the
DLC film.
Fig. 2(f) presents the metallography of the sample NIT80+­
GRAD+DLC, in which it is possible to observe the presence of a DLC film
with a thickness of 2.23 μm indicated by the black line and a compound
layer with a thickness of 6.62 μm, pointed by the red line. This com­
pound layer is thicker when compared to other nitriding treatments, as
the gradient process performed following the nitriding treatment in­
creases the diffusion of nitrogen and carbon in the material, facilitated
by the low ionization energy of the methane compounds [37].
There was observed a large difference in the hardness result between
the samples that presented DLC film adhered to the substrate (samples
DLC, NIT05+DLCw, NIT80DLCw, and NIT80+GRAD+DLC) compared
to treatments that presented DLC film delamination (samples
NIT05+DLCw/0 and NIT80DLCw/o). As observed in Fig. 6(b), the su­
perficial hardness of the NIT05+DLCw and NIT80+DLCw sample was
above 1100HV, while in the sample NIT80+DLCw/o, in which the DLC
film delaminated, presented a hardness around 600HV. In addition to
the fact that the hardness is higher in samples in which the DLC film
9
Surfaces and Interfaces 36 (2023) 102352
presented good adhesion to the substrate, it is also possible to analyze
that diffusion zones were thicker in samples in which the treatment had
more nitrogen during nitriding, as observed previously [8].
The sample NIT80 + DLCw presented the highest superficial hard­
ness, with a value of 1178HV, slightly higher than sample NIT80+­
GRAD+DLC, with a hardness of 1021HV. It is explained by the adhesion
test results observed in Fig. 12(e), in which the adhesion classification of
the NIT80+GRAD+DLC sample was HF2, inferior when compared to
sample NIT80+DLCw, classified as HF1. However, although the classi­
fication of sample NIT80+GRAD+DLC was inferior to sample
NIT80+DLCw, both are acceptable according to VDI 3198 standard and
determine a DLC film with good adhesion on a metallic substrate. This
result is justified by the flow gradient, which allows a smooth difference
between the composition of the composite layer produced in the ther­
mochemical treatments and the DLC film, guaranteeing a good inter­
action between them and consequently a good adhesion of DLC film on
the substrate without using conventional organosilicon interlayer. This
result was also found by Cho et al. [38], where the deposition of a
functionally gradient DLC was deposited on AISI 316-L stainless steel
and increased the adhesion strength between the film and the substrate.
Table 5 shows the results of the hardness and thickness of DLC films,
compound layers, and diffusion zones of the multilayer treatments. It is
possible to observe that in the samples which present good adhesion of
DLC film on a metallic substrate, the hardness is superior to 900HV.
Diffusion zones are correlated with nitrogen potential used during
treatments, in which higher potential produced a thicker diffusion zone,
except for sample NIT80+GRAD+DLC, which presented a thinner
diffusion zone due to the decrease of the nitrogen percentage during the
treatment. The treatments NIT05+DLCw/o and NIT80+DLCw/o pre­
sented similar behavior to simple nitriding treatments once the DLC did
not influence the results due to there was not a good adhesion of this film
on the substrate.
Wear results of the untreated and multilayered samples are shown in
Fig. 7(b). It is possible to observe that all treatments presented lower
wear volume when compared to the base material, showing the effi­
ciency of the multilayer treatments. The samples that presented a higher
wear volume did not have good adhesion of the DLC film on the sub­
strate. This is justified by the fact that when the film has detached from
the sample, the wear volume should not be related to the film, but to the
substrate or the compound layer on the surface of the steel. Thus, the low
adhesion of DLC films on the substrate has impaired the wear resistance
compared to samples with good adhesion of the film on the treated
metal, since there was no film to improve wear resistance [11].
The sample NIT80+DLCw showed one of the lowest wear volumes
justified by a combination of the high hardness provided by C-C sp3
hybridizations and the low coefficient of friction from DLC film, the high
hardness of the compound layer, and hardness in depth provided by the
diffusion zone. This result was also found by Dalibon et al. [39] and
Kovaci et al. [40]. The opposite happened with the NIT05+DLCw
sample, in which the absence of a compound layer impaired the wear
behavior of the material and promoted a greater wear volume compared
to the other treated materials. However, all multilayer treatments
improved the wear resistance compared to untreated material.
The sample NIT80+GRAD+DLC presented the lowest wear volume,
similar to sample NIT80+DLCw. This result can be related to the com­
bined effect of the DLC film and the integrity of the compound layer
without defects and cracks. Furthermore, the presence of carbon in­
creases the hardness of the layer and also improves the adhesion of DLC
film on the substrate without the necessity of an organosilicon interlayer
[41]. It is also possible to explain by the high presence of ε nitride,
observed in Fig. 5, promoted by the presence of a high quantity of car­
bon in the compound layer, which increases the ductility of the layer,
increasing the wear resistance [42]. Similar results were found by de
Campos et al. [12]. This result indicates that the silicon interlayer is not
obligatory to obtain high wear resistance when the good adhesion of
DLC film on the substrate is achieved by other techniques, as observed
M.R. Danelon et al. Surfaces and Interfaces 36 (2023) 102352

Fig. 11. Topography of the surfaces after corrosion test (A) MB, (B) NIT05, (C) NIT80, (D) DLC, (E) NIT05+DLCw, (F) NIT80+DLCw, (G) NIT80+DLCw/o, and (H)
NIT80+GRAD+DLC.

10
M.R. Danelon et al.
Fig. 12. Adhesion test results of samples (A) DLC, (B) NIT05+DLCw, (C) NIT80+DLCw, (D) NIT80+DLCw/o, and (E) NIT80+GRAD+DLC.
for the multilayer treatments by a gas flow gradient, that can be used as
other option for obtaining an adequate adhesion of the DLC film on the
metallic substrate.
Analyzing the wear modes of multilayer treatments, it is possible to
observe a similar behavior to simple treatments. Samples with wear
volume higher than 5,0 × 10− 3 mm3 presented grooving wear mode, due
to a test with high load and low presence of abrasives, while samples
with wear volume lower than 5,0 × 10− 3 mm3 have shown mixed wear
mode (grooving+rolling), since there was a compound layer and a thin
film which debris come off the surface of the samples, acting like an
abrasive [29].
An interesting detail to observe in samples that have presented a
compound layer and good adhesion of DLC film (NIT80+DLCw and
NIT80+GRAD+DLC), presented mixed wear mode but with a higher
tendency to rolling wear mode, observed in Fig. 8(c). This can be
explained by the presence of a thin film on the surface of the samples,
11
Surfaces and Interfaces 36 (2023) 102352
which may increase the debris quantity coming off the sample during the
test that rolls in the wear region [29].
These results also corroborate with Kusano and Hutchings [31] re­
sults, which say that rolling wear mode presents a lower coefficient of
friction when compared to grooving wear mode, since DLC films are well
known that reduces the coefficient of friction of samples, and the sam­
ples which have presented the best wear resistance are the ones which
presented the best performance in adhesion tests [43].
Corrosion test results of the untreated and the samples with multi­
layer treatments are presented in Fig. 9(b). It is interesting to observe
that the highest Ecorr (-0.165 V) and the lowest icorr (2.096 × 10− 10 A/
cm2) were obtained to the sample NIT80+DLCw, which presented an
adequate DLC film adhesion and the formation of the compound layer. A
combination of the DLC film and a nitride layer with an organosilicon
interlayer significantly improves the corrosion resistance of the mate­
rial, requiring more energy for the pit formation and providing less
M.R. Danelon et al.
aggressive corrosion phenomena to the material.
The treatment NIT80+GRAD+DLC showed Ecorr of -0.270 V. Despite
being similar, the sample NIT80+GRAD+DLC presented a higher icorr
than the sample NIT80+DLCw, indicating a worse anticorrosion
behavior, but better compared to the other treatments studied. The DLC
film did not present adequate adhesion in the metal surface to the
sample NIT80+DLCw/o, however, the compound layer ensured a better
corrosion performance when compared to the base material, presenting
Ecorr of -0.384 V.
This result is explained by de Campos et al. [12], in which the
compound layer together with DLC forms a barrier that provides low
interaction with ions, making the corrosion process difficult. Despite the
DLC film presenting some defects which allow the fluid to pass through
the film, the compound layer maintains the anticorrosive barrier,
increasing the corrosion resistance of the sample submitted to the
multilayer treatment. The absence of a compound layer on the surface of
the material significantly impairs the corrosion resistance of the treated
metal, as can be observed in samples NIT05+DLCw and
NIT05+DLCw/o, which have shown Ecorr of -0.671 V and -0.958 V
respectively.
It is possible to observe in the polarization curve presented in Fig. 9
(b) the presence of metastable pits in the samples NIT80+DLCw and
NIT80+GRAD+DLC, which may be related to the presence of pre­
cipitates on the surface of the material, where the pit has enough energy
to propagate along with the precipitate, but not enough energy to
remove it [44,45].
The adhesion test results of the samples NIT05+DLCw,
NIT80+DLCw, NIT80+DLCw/o, and NIT80+GRAD+DLC are shown in
Fig. 12(b), (c), (d), and (e), respectively, that corroborate with the
metallography and wear results. The sample that did not show an
acceptable adhesion of DLC film on the sample was NIT80+DLCw/o,
classified as HF6 according to VDI 3198 standard, and the low adhesion
is justified by the absence of an interlayer or gradient between the film
and the nitrided surface. The samples NIT05+DLCw, NIT80+DLCw, and
NIT80+GRAD+DLC showed acceptable adhesion, classified as HF4,
HF1, and HF2, respectively.
Fig. 11 shows the surface analysis of samples after the cyclic polar­
ization test, in which the sample NIT80+DLCw presented lower pits
quantity. This is justified by the combination of the DLC film and a
compound layer, which provide greater corrosion resistance to the
studied material. Although the sample NIT80+DLC presented lower pits
quantity compared to sample NIT80+GRAD+DLC, it is possible to
observe a low amount in both treatments. On the other hand, the sample
NIT05+DLCw did not present a compound layer and presented a great
number of pits on the surface. The sample NIT80+DLCw/o presented
intermediated corrosion resistance, explained by the difficulty of
adhesion of the DLC on the surface.
4. Conclusion
With the development of this work, it was possible to observe the
efficiency of surface treatments on the wear and corrosion resistance of
AISI 4340 steel.
Analyzing the results obtained by the nitriding treatments, we can
observe that regardless of the compound layer formation, the wear
resistance of the material is improved by nitriding treatment. It is also
important to note that the compound layer proved essential to
improving the corrosion resistance of the studied material, in which the
ceramic characteristic of the layer makes the corrosion difficult.
The deposition of the DLC film on the material improved both the
wear and corrosion resistance of AISI 4340 steel. Its high hardness
provided an increase in the wear resistance of the material and the
chemical inertia increased the Ecorr and decreased the icorr of the ma­
terial studied improving its corrosion resistance.
It was possible to observe that the DLC film adhesion is a funda­
mental factor in significantly improving the wear and corrosion
12
Surfaces and Interfaces 36 (2023) 102352
resistance of the studied material. Then, the limitation of the applica­
tions and properties of the DLC film deposited on a surface metal is the
adhesion of the film on the substrate, giving rise to the necessity to use
an interlayer between the DLC film and the treated surface. Another
alternative to improve the adhesion of the DLC film on the metal surface
was presented in the sample NIT80+GRAD+DLC, in which the gas flow
gradient provided a good interaction between the compound layer and
the DLC film, reducing tensions and providing a good adhesion of the
film over the substrate without the need of an interlayer between the
substrate and the film.
Although the sample NIT80+GRAD+DLC did not present the best
performance in all tests performed, it showed extremely superior
properties when compared to the base material and similar properties to
the NIT80+DLCw treatment, proving the efficiency of the gradient
treatment, as it achieved properties similar using a different technique.
These results show the possibility of performing a multilayer treat­
ment with standard gases of nitriding and deposition of DLC film,
without the use of different gases, solid targets, or liquid precursors to
obtain good adhesion of the film on the substrate and still obtain
interesting tribological and corrosion properties to the material. This
technique can be an advantage for automated equipment used in the
industrial sector.
It is concluded that it is possible to carry out a multilayer treatment
without the necessity of an interlayer based on silicon or other elements
that are not part of conventional treatments such as nitriding and DLC
film deposition, which still provide good adhesion of the DLC film on the
substrate and improve tribological and corrosion properties of metals,
facilitating the industrial production of large-scale treatments.
CRediT authorship contribution statement
Miguel Rubira Danelon: Conceptualization, Investigation, Writing
– original draft, Visualization. Larissa Solano de Almeida: Conceptu­
alization, Investigation, Writing – review & editing. Marcos Dorigão
Manfrinato: Writing – review & editing, Resources, Supervision.
Luciana Sgarbi Rossino: Conceptualization, Resources, Writing – re­
view & editing, Supervision, Project administration.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data Availability
No data was used for the research described in the article.
Acknowledgments
The authors gratefully acknowledge the financial support from the
São Paulo Research Foundation FAPESP (2019/13041-3), Physics
Institute of University City “Zeferino Vaz” – UNICAMP, and LapTEC
located at UNESP – Campus Sorocaba by laboratory facilities.
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