Surface & Coatings Technology 464 (2023) 129542

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Surface & Coatings Technology

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Full Length Article

Time-resolved plasma diagnostics of cathodic cage plasma nitriding system

with variable pulsed duty cycle and surface modification of plain
carbon steel
M. Naeem a, *, Madiha Qadeer a, Zaka-ul-islam Mujahid b, N.U. Rehman c, J.C. Díaz-Guillén d,
R.R.M. Sousa e, M. Shafiq f
a
Department of Physics, Women University of Azad Jammu and Kashmir Bagh, Pakistan
b
Department of Electrical Engineering and Information Science, Ruhr-University Bochum, D-44780 Bochum, Germany
c
Department of Physics, COMSATS Institute of Information Technology, Park Road, Islamabad 44000, Pakistan
d
CONACYT, Mexican Corporation for Materials Research, Saltillo, Coahuila, Mexico
e
LIMAV, Postgraduate Program in Materials Science and Engineering - Federal University of Piaui (UFPI), Teresina, PI, Brazil
f
Department of Physics, Quaid-I-Azam University, Islamabad, Pakistan

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

Keywords: Cathodic cage plasma nitriding (CCPN) is an efficient technique to improve the surface properties of metallic and
Electron temperature non-metallic materials, including steels. Usually, CCPN is powered by pulsed voltage sources due to additional
Hardness control of the nitrided layer's thickness and composition as well as the discharge transition to the arc region can
Wear
be controlled by varying the pulsed duty cycle. As the behavior of pulsed plasma varies with time, it is important
ICCD
to monitor variation in plasma parameters by using time-resolved plasma diagnostics. Unfortunately, the
Corrosion
fundamental time-resolved diagnostics of such discharges are still very limited. Here, we report time-resolved
measurements of current, voltage, plasma emission, space, and time-resolved emission from a single hole in
the cathode as a function of pulsed duty cycle (15–75 %) at constant total current. The results show that the
electron temperature is higher if a higher peak current and the shortest 15 % pulsed duty cycle are used. The
results obtained from plasma diagnostics are confirmed by treatment of plain carbon steel samples in identical
conditions and found that the best hardness, wear, and corrosion resistance is obtained at the lowest pulsed duty
cycle. The study suggests that plasma generated at a low pulsed duty cycle and a higher peak discharge current
exhibits higher electron temperature and less fluctuations in plasma emission which are more efficient in
attaining high surface hardness, better wear, and corrosion resistance to nitride plain carbon steel.

1. Introduction cathode. However, this arrangement limits the maximum current and
power beyond a specific level; the higher ion bombardment can damage
The surface properties of iron alloys can be modified by thermo­ the samples due to significant sputtering [3]. Further, the direct
chemical diffusion techniques, such as nitriding, in which nitrogen bombardment of ions on the samples can cause over-heating of samples,
atoms are diffused in the material at a suitable temperature [1]. Initially, non-uniform nitriding, and edge effect. These limitations of the CPN
conventional nitriding techniques, including salt-bath nitriding and gas restrict the extent of performance improvements for industrial
nitriding, were introduced, which are not eco-friendly, and thus their applications.
use is reduced in industrial sectors [2]. Later on, these conventional Almost two decades ago, a new plasma nitriding concept was
nitriding techniques were substituted by plasma nitriding technique, introduced where the samples are floating or separately biased while the
also known as ionitriding or conventional plasma nitriding (CPN), which discharge is ignited between the outer grounded chamber (anode) and a
remained active for surface modification of steels for several decades. concentric inner perforated cathode to break down the gas [4]. The
The CPN arrangement has a grounded chamber acting as an anode and concept is named in the literature as active screen plasma nitriding and
samples at the cathodic potential, generates ion bombardment at the cathodic cage plasma nitriding (CCPN) [5]. Intense plasma is generated

* Corresponding author.
E-mail address: [email protected] (M. Naeem).

https://doi.org/10.1016/j.surfcoat.2023.129542
Received 9 October 2022; Received in revised form 6 March 2023; Accepted 15 April 2023
Available online 25 April 2023
0257-8972/© 2023 Elsevier B.V. All rights reserved.
M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 1. Schematic representation of cathodic cage plasma nitriding reactor, magnelab current transformer, and plasma diagnostics.

fundamental mechanism of CCPN was proposed in several models,

Table 1
including Hubbard et al. [6–8], Zhao et al. [9], Li and Bell [10], Gallo
Effect of pulsed duty cycle on corresponding voltage and peak discharge current.
and Dong [11], Saeed et al. [12], and Fraczek et al. [13]. In these
Duty cycle Active pulsed time Voltage Peak discharge current models, it is proposed that in addition to the reactive nitrogen species,
(%) (μs) (V) (A)
cathodic cage material (iron, iron nitrides, and other cathode constitu­
15 3.75 600 7.5 ents) can be sputtered in CCPN and then re-deposited on the surface of
30 7.5 550 4
the sample. Due to this additional feature of cathode cage material
45 11.25 500 2.6
60 15 417 1.8 deposition, CCPN can deposit specific materials at the sample surface
75 18.75 400 1.4 and tailor and enhance the properties for different applications, such as
the introduction of metals at the surface of polymers [14]. As reported in
the literature [15–18], the plain carbon steel samples are unsuitable for
in each hole (hollow cathode effect) while transporting the reactive nitriding due to the absence of nitride-forming elements (such as Cr, Al,
species to the inside samples. In CCPN configuration, much higher Ni). As AISI-304 austenitic stainless steel cathodic cage contains an
powers can be used without sputtering or damaging the samples. The abundant amount of Cr, and thus it enables the nitriding and improves

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 2. Time-resolved variation of pulsed current and corresponding emission intensity at different pulsed duty cycles (15–75 %).

the nitriding performance of plain carbon steel [19]. compared for surface modification of plain carbon steel (St-37) in terms
Several power sources can generate plasma, depending upon the of hardness, wear resistance, and corrosion resistance.
required application, including DC discharges, pulsed DC discharges, RF
discharges, and microwave discharges [20,21]. As reported, the 2. Experimental details
nitriding system is commonly operated by DC power sources [21].
However, the pulsed DC discharges are preferred due to additional This work aims to investigate the effect of the pulsed duty cycle on
control on nitriding performance by changing the pulsed frequency or time-resolved plasma parameters and the nitriding performance of the
pulsed duty cycle [22,23]. In pulsed DC glow discharges, the sputtering cathodic cage plasma nitriding (CCPN) system. The CCPN system con­
by ions bombardment is effective during the active pulse (on time of a sists of a grounded (anode) stainless steel reactor of 31.5 cm diameter
pulse TON ), whereas the active species of plasma is retained during the and 33.5 cm height, austenitic stainless steel perforated cage as a
whole cycle (T = TON + TOFF ) [24]. Thus, it is important to examine the counter electrode (cathode), as shown in Fig. 1(a). The cage was made
effect of the pulsed duty cycle (TON /(TON + TOFF ) ) on time-resolved up of a 2 mm thick AISI-304 steel sheet with uniformly punched holes of
plasma parameters and nitriding performance. 8 mm diameter on the sidewalls and 6 mm on the top lid. The samples of
Several authors reported the effect of the pulsed duty cycle on plain carbon steel (St-37 grade with a composition (Wt%) 0.11C, 0.56
various substrates in a conventional plasma nitriding system. It includes Mn, 0.03 Si, 0.005 S, 0.005 P, 0.03 Ni, 0.07 Cr, and balance Fe) were
Menthe and Rie [25] on nitriding of AISI-304 steel, Alves et al. [22] on treated at 400 ◦ C temperature for 4 h at a floating potential, and samples
AISI-409 steel, Díaz-Guillén on AISI-4340 steel [26], Taherkhani and were kept at a vertical distance of 55 mm from cage lid. The plasma was
Mahboubi [27] on AISI-H13 steel, and they reported a significant effect generated at an optimum pulsed frequency of 40 kHz, filling pressure
of pulsed duty cycle on nitriding performance. However, the effect of the 150 Pa, gases composition of N2/ H2 (3/ 2) with a total flow rate of 50
pulsed duty cycle on CCPN is limited in the literature. Previously we sccm, and a small amount of argon gas was added as an actinometer (4
reported the effect of the pulsed duty cycle on nitriding of austenitic %).
stainless steel AISI-304 and AISI-316 and observed that hardness, wear A self-assembled triple Langmuir probe (TLP), made up of tungsten
resistance, and corrosion resistance can be improved by tuning the wires and operated by a variable DC voltage source (0–500 V), was used
pulsed duty cycle [28,29]. As in the pulsed DC glow discharges, plasma's to measure the time-resolved electron temperature. The tungsten wires
behavior varies rapidly, depending upon the frequency of the power of 0.38 mm diameter, tip length of 5 mm, and wires separation of 1 mm.
source, the plasma is turned on and off in a few nano-second to micro- The time-resolved changes in electron temperature were measured by
seconds time, and for better understanding, time-resolved plasma di­ the differential probe and digital storage oscilloscope, as reported by
agnostics is required. Particularly, the time-resolved plasma diagnostics Qayyum et al. [30]. On a digital storage oscilloscope, the time-resolved
of such discharge are still limited. changes in peak discharge voltage and current were also monitored by
In this work, a combination of current and voltage, photomultiplier, high voltage probe Testec Hvp-15HF and Magnelab Current transformer
the triple Langmuir probe and ICCD camera are used for time-resolved CT-E1.0-BNC, respectively. The corresponding time-resolved changes in
plasma diagnostics to examine variations in plasma with a pulsed duty emission from the plasma were monitored by a photomultiplier tube.
cycle (15–75 %). The time-dependent variation in peak current is The space and time-resolved emission from the cathodic cage are
observed and compared with emission from plasma and electron tem­ measured using an Andor intensified charge-coupled device (ICCD)
perature. In addition, the effect of the pulsed duty cycle on nitrogen camera and an interference filter to image nitrogen 391 nm emission
atomic and molecular species density is monitored by optical emission line. The line is significantly excited from the ground state nitrogen
spectroscopy. Finally, the results obtained from plasma diagnostics are atoms with a threshold of 18.7 eV [31]. The camera is focused on the

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 3. Time-resolved variation of electron temperature measured by triple Langmuir probe at different pulsed duty cycles (15–75 %).

single hole of the hollow cathode with a lens and imaged using a Thorlab delay in the internal delay generator of the camera. The camera only
optical emission filter with 390 nm center wavelength and 10 nm images a single image at each time step. The emission from the center of
bandwidth, as shown in Fig. 1(b). The camera is externally triggered and the single image is horizontally binned and plotted as a function of time.
synchronized by the high voltage pulse from the voltage probe using a Further details about the PROES are discussed in the following papers
TTi pulse/signal generator. The images are acquired with a 0.1 μs time [32–34]. The space averaged optical emission spectroscopy (OES)
resolution during the whole voltage pulse and beyond by varying the analysis was conducted by a high-resolution spectrometer, and its

4
M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 4. Time-resolved evaluation of plasma emission recorded by the ICCD camera at various pulsed duty cycle (a) 15 %, (b) 30 %, (c) 45 %, and (d) 60 %.

Fig. 5. Time-resolved evaluation of plasma emission recorded by the ICCD camera at various peak currents by keeping 15 % duty cycle (a) 4 A (b) 5 A (c) 6 A (d) 7 A
(e) 8A.

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

( [ ])
Fig. 8. Variation of nitrogen active species density [N], N+
2 as a function of
pulsed duty cycles (15–75 %).

Fig. 6. Emission spectra of nitrogen bands and argon line in the wavelength
range (365–430 nm) at various pulsed duty cycles (15–75 %).

Fig. 9. Microhardness profile of nitrided plain carbon steel samples at various

pulsed duty cycles (15–75 %).

method reported in previous work [36].

Fig. 7. Variation of normalized emission intensities corresponding to nitrogen
line, iron line, and nitrogen bands as a function of pulsed duty cycles. 3. Results and discussion

3.1. Time-resolved variations in plasma

details about data acquisition and analysis can be found in the previous
report [35].
Here the cathodic cage plasma nitriding system is operated by a
The surface properties of nitrided samples were assessed by
pulsed DC voltage source, and thus the behavior of plasma changes with
numerous techniques: the surface hardness was obtained by Vickers
pulse variation. Therefore, the time-resolved evaluation of plasma pa­
microhardness tester using dwell-time of 5 s, normal load of 10 gf, and
rameters is reliable for understanding the pulsed duty cycle's effect on
measurements were repeated 8 times to minimize the measurement
the plasma characteristics. Several authors reported in various systems
error. The phases' structure was monitored by X-ray diffraction tech­
that tuning pulse width could improve the processing efficiency: Butler
nique with CuKα radiation. The surface morphology and thickness of the
et al. [37] reported that the deposition rate in high power impulse
deposited layer were examined by scanning electron microscopy. The
magnetron sputtering (HIPIMS) could be increased by using the shorter
wear test was conducted by a dry ball-on-disc wear tester with condi­
pulse length. It can increase the peak discharge current, thus main­
tions described elsewhere [36]. Finally, the corrosion resistance of
taining the high ionized flux. They proposed that in the afterglow (when
nitrided samples was examined by a potentiodynamic polarization plot
the pulsed voltage is off), the target potential is zero, and thus the back-
using a 3.5 % NaCl solution, following the conditions and data analysis

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

sheath collapses; as a result, the hot electrons in the plasma are not
confined [38]. The loss of these hot electrons from plasma can cause an
increase in plasma potential during the pulse-off time. This increase in
plasma potential can cause a burst of energetic ions toward the substrate
and can also increase the electron temperature [38].
The space and time-resolved changes in the discharge structure can
be observed in PROES data in Fig. 4. It shows that discharge is intensely
luminous in the center, indicating the bulk, and less intense at the top
and bottom, indicating the sheath. All the measurements have been
normalized; therefore, they only provide the relative luminosity
changes. The sheath width shrinks with the increase in the plasma
density and vice versa. For all the results here, a similar peak current is
used. The peak current has been varied in Fig. 5, where the duty cycle
has been kept constant. The electron temperature results show an
intense electron temperature in the beginning pulse, which drops later
and usually saturate at lower values. During the whole pulse, the sheath
width and the electron density fluctuate. The origin of such change is not
understood and could be because of instability. This could be similar to
past measurements of kHz time scale instabilities [43]. The creation of
instabilities in discharge can be associated with the changes in electron
Fig. 10. X-ray diffraction pattern of nitrided plain carbon steel samples at temperature and electron number density as a source of the disturbance.
various pulsed duty cycles (15–75 %). When the electron temperature is decreased in the plasma, it can reduce
the ionization rate in the discharge and the resultant decrease in electron
attraction electric field for ions vanishes. Breilmann et al. [38] investi­ number density. In this case, the disturbance could be balanced, and no
gated the effect of pulse width on high-power impulse magnetron instability will exist in the plasma, referred to as negative feedback, as
sputtering of titanium. They observed that when the plasma is switched reported [44]. However, in the case of electronegative discharge, a
off in the pulse voltage, the target sheath collapses; therefore, the plasma decrease in electron temperature can cause an effective increase in
environment's hot electrons are not confined. Due to the loss of these hot electron density when the attachment rate is strongly reduced than the
electrons from plasma, the plasma-potential increases soon after the ionization rate. This increase in electron number density due to a
plasma is switched off. This increase in plasma potential can cause a decrease in electron temperature is referred to as positive feedback and
burst of energetic ions toward the substrate. is responsible for instability in plasma [44–46]. This aspect should be
Considering the above discussion, we investigated the effect of the investigated further in the future. The comparison of Figs. 3 and 4 shows
pulsed duty cycle by keeping the time average current as a fixed a discrepancy in behavior of plasma observed by PMT and ICCD camera,
parameter instead of pulsed power. The external heater is used beneath which can be attributed as: the ICCD shows the light from a single hole,
the sample holder to maintain the processing temperature. This through a filter, and thus it indicates energetic electrons. On the other
approach is also recently reported for plasma oxidation by varying the hand, PMT shows light from overall emission from plasma.
pulsed duty cycle at constant pulsed current density, and they found a The emission has been investigated further for only 15 % duty cycle
significant effect of the pulsed duty cycle on oxidation performance in Fig. 5 as a function of peak current. The measurements show that at
[39–41]. In this study, we kept the time average current at a constant 4A peak current, the discharge has one weak structure at the start and
value of 1.2 A (the maximum available current at which stable discharge two follow-up stronger emission structures during the pulse. With the
is obtained), and the pulsed duty cycle varied from 15 % to 75 %, and increase in peak current, the fluctuations decrease and the two strong
corresponding changes in peak current and peak voltage are observed as structures are merged together (at 8 and 9A). The lower fluctuations in
provided in Table 1. It shows that while changing the duty cycle, the emission at higher currents show that the discharge is more stable and
corresponding change in peak current is significant, while voltage is uniform in these conditions. Also, the increase in peak current increases
changed in the 400–600 V range. The time-resolved variation in emis­ the width of the emission structures and decrease in the sheath width,
sion from plasma and the corresponding peak current is shown in Fig. 2. which indicates a higher electron density at higher currents.
It shows that emission intensity from plasma, which indicates energetic Thus, the time-resolved ICCD imaging depicts that at a low duty
electrons in the plasma, is highest for the 15 % pulsed duty cycle and cycle and higher peak discharge current, an intense and more stable
lowest when plasma is generated at 75 % pulsed duty cycle. The emis­ discharge is generated in each hole of the cathode. These observations
sion intensity corresponds to the peak current rather than the total are qualitative in nature; however, they provide important information
current. During the pulsed-on time (as the negative cycle is used for regarding the time resolved characteristics of the discharge in each hole
plasma generation, thus the negative cycle is the active cycle), the of the cathode.
emission from plasma increases and achieves a maximum and stays
constant for the higher duty cycle after the maximum emission, which
decays linearly with the pulse off time and starts increasing with the next 3.2. Optical emission spectroscopy diagnostics
pulse. The emission corresponds with the measurement of flux and
sputtering in HIPIMS reported in the literature [38,42]. The space averaged optical emission spectroscopy qualitatively
Fig. 3 shows the measured time-resolved variation in electron tem­ measures the plasma active species density. The spectra recorded for the
perature using a triple Langmuir probe. It depicts that at a higher duty first negative system of nitrogen N2+ and second positive system of ni­
cycle (45–75 %), the electron temperature has a sharp peak in the trogen N2 in the spectral range of 365–430 nm at various duty cycles are
beginning and later drops to lower values and is significantly lower presented in Fig. 6. The normalized emission intensities of various ni­
during the passive time of pulsed current (pulse-off time). In contrast, at trogen lines, iron lines, and nitrogen bands as a function of the pulsed
a low duty cycle (15–30 %), the electron temperature does not drop from duty cycle are presented in Fig. 7. It depicts that emission intensities
the initial sharp peak, and electron temperature slowly drops during the drop with the increase in the pulsed duty cycle. Also, the nitrogen active
[ ]
pulse-off time. This dependence of electron temperature on the pulsed species density [N], N+2 presented in Fig. 8 shows a decrease with an
duty cycle can be ascribed as: when the plasma is switched off, the target increase in the pulsed duty cycle. These results are in agreement with a

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 11. Surface (along with corresponding EDS) and cross-sectional SEM images of nitrided plain carbon steel samples at different pulsed duty cycles (a, b) 15 %,
and (c, d) 30 %.

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 12. SEM images of wear tracks of plain carbon steel samples along with wear rates (a) untreated, (b) 15 %, and (c) 30 %.

time-resolved variation of electron temperature described in the above be achieved. In contrast with CPN, the CCPN involves the deposition of
section. Therefore, higher quantities of nitrogen-active species are cathodic cage sputtered material on the floating samples, and thus using
generated at a higher current where higher electron temperature is a cathodic cage of some specific material containing nitride-forming
observed. Furthermore, the iron line increases, indicating that the elements can be used to improve nitriding performance. Here, an
sputtering increases with the current. Thus, the nitrogen active species austenitic stainless steel cathodic cage is used, which contains sufficient
density and cathodic cage sputtering increase at a shorter pulse with a chromium contents, and thus significant improvement in hardness is
higher peak current. obtained. At the lowest duty cycle, the peak discharge current is
maximum, which can cause more sputtering from the cathodic cage, and
also nitrogen gets dissociated by electron impact dissociation, and thus
3.3. Surface modification of plain carbon steel iron nitride is deposited on the sample surface, which can be confirmed
by structural analysis. The higher sputtering at the low duty cycle can be
The plasma nitriding of plain carbon steel is performed in compa­ ascribed to the loss of hot electrons during the pulse-off time [38]. It
rable conditions to the plasma diagnostics. The surface hardness of plain increases plasma potential, and the sheath in front of the substrate ex­
carbon steel is analyzed and presented in Fig. 9. The hardness of plain pands toward the bulk of the plasma. Thus, the ions experience an
carbon steel (~150 HV) is enhanced to ~500–900 HV, and a maximum electric field due to the plasma sheath expansion, and a burst of ions
hardness is obtained at the lowest duty cycle, which agrees with results reaches the cathode.
obtained from plasma diagnostics. The literature [15–18] reports that The incorporation of nitrogen atoms in the sample surface is higher
conventional plasma nitriding of plain carbon steel cannot achieve at the low-duty cycle; it can cause higher stresses on the sample surface
satisfactory hardness due to the absence of nitride-forming elements and increase strain levels [47]. This increase in strain level is responsible
(like chromium, aluminum, vanadium, and molybdenum). When for the highest surface hardness. The surface hardness reported here is
nitride-forming elements are absent, reasonable surface hardness cannot

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fig. 13. Anodic polarization corrosion curves of untreated and nitrided samples.

higher than reported literature on plain carbon steel, such as Ashrafi­ structure, in which iron atoms lie on the corner of the cubic structure
zadeh et al. [48] 470 HV, Nakata et al. [17] 400–800 HV by additional and the faces site, and nitrogen atoms lie at the octahedral site [50]. The
treatment for alloying elements deposition, and Madanipour et al. [16] higher surface hardness at low duty cycle can be ascribed to the domi­
760 HV by additional aluminum deposition and long-processing time. It nant presence of Fe3 N having hcp structure, in which the number of slip
shows that the pulsed DC CCPN system can be used effectively for the planes is less than the number of slip planes in fcc structure, and thus
surface hardness of plain carbon steel, specifically if operated at a low- there is less probability of deformation under the normal loads.
pulsed duty cycle. The nitrided layer is examined by scanning electron microscopy
The structural composition of nitrided steel samples by X-ray (SEM), and surface and cross-sectional SEM images are presented in
diffraction is presented in Fig. 10. The XRD pattern of the base sample Fig. 11. The surface of nitrided samples (Fig. 11 a, c) depicts the pres­
shows the presence of the α‑iron phase, whereas, after plasma nitriding, ence of uniformly distributed particles, which are agglomerated in
these peaks appear to diminish due to the formation of the iron nitride bunches. These particles are of iron nitrides, which are deposited due to
layer. The sample nitrided at low duty cycle shows that iron peaks are iron sputtering from the cathodic cage and its combination with nitro­
suppressed due to better conversion of the skin layer to iron nitrides. The gen atoms, as presented in several models of CCPN [11,12]. This state­
nitrided samples show the presence of added phase of iron-nitrides ment is supported by corresponding EDS spectrum, which shows the
(Fe4 N, Fe3 N) and iron nitride phases are intense for sample nitrided at presence of iron, chromium and nitrogen on the treated sample. The
low-duty cycle. It indicates the formation of a thick nitrided layer under additional presence of chromium depicts that it is deposited due to
this condition. The improvement in hardness can be ascribed to the sputtering from cathodic cage, as discussed in the introduction. The
formation of iron nitrides, which is harder than iron. However, the cross-sectional SEM images (Fig. 11 b, d) show the formation of 2.8 μm
difference in hardness with the duty cycle can be credited to the crystal and 1.38 μm thick layers by keeping a duty cycle of 15 % and 30 %,
structure of Fe4 N and Fe3 N nitride phases. As Fe3 N exhibits layers of iron respectively. This formation of a thick nitrided layer at a low duty cycle
and nitrogen as Fe − N − Fe − N − Fe, where nitrogen atoms play the role can be attributed to the higher peak current under this condition, as
of spaces along the c-axis of hexagonal closed pack (hcp) structure of described earlier.
iron sublattice [49]. In contrast, Fe4 N have a face-centered cubic (fcc) The wear performance of nitrided plain carbon steel samples is

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

Fe3 N, which contains higher amount of nitrogen [54].

4. Conclusions and final remarks

Here, plasma is diagnosed by triple Langmuir probe, PROES, and

optical emission spectroscopy (OES), and obtained results are confirmed
by processing plain carbon steel samples in identical conditions. The
conclusions are as follows:

1. The time-resolved changes in electron temperature obtained by the

triple Langmuir probe show that electron temperature is higher at
the low pulsed duty cycle. Furthermore, the temporal variation in
electron temperature matches the variation in peak discharge cur­
rent at a constant time average current.
2. The ICCD images of a single cathode hole shows time resolved
fluctuation in emission as multiple structures during the applied
pulse, which indicates instabilities. Using a low duty cycle and higher
peak current, the multiple emission structures are merged indicating
lower fluctuations. Simultaneously, the width of the structure in the
cathode hole increases and sheath width decreases indicating a
higher electron density. As a result, the time averaged active species
density monitored by optical emission spectroscopy (OES) is also
higher if a short pulse with higher peak current is used compared to
Fig. 14. Corrosion rates of untreated and nitrided samples. longer pulse with lower peak current.
3. The effect of pulsed duty cycle on plasma parameters is confirmed by
assessed by a ball-on-disc wear tester, and worn tracks are presented in plasma nitriding of plain carbon steel samples in identical condi­
Fig. 12. The worn track of base material (Fig. 12 a) is relatively wide, tions. The hardness, wear resistance, and corrosion resistance are
having deep grooves and a ridge-like pattern. This severe wear of base maximum when nitriding is performed at a low pulsed duty cycle,
material can be attributed to the plastic deformation and micro-plowing following the results obtained from plasma diagnostics.
due to its low hardness. In addition, the track exhibits metallic debris,
and microcracks are induced during the sliding of the ball against the This study shows that the time-resolved plasma diagnostics by TLP
sample, and thus it reveals the existence of an abrasive wear mechanism. and ICCD camera and active species density by OES are in good agree­
The worn tracks of nitrided samples are presented in Fig. 12 b, c, which ment with the surface properties of nitrided plain carbon steel, and thus
shows that the tracks are relatively narrow and smooth, and no cracks or these diagnostics can be used efficiently for system optimization.
metallic debris appear on the track. The wear rates presented in Fig. 12 Further, it shows that by keeping the time average current at some
also show a significant decrease in wear rates by plasma nitriding, constant value, a short high peak current pulse provides better surface
specifically for sample nitrided at a low pulsed duty cycle. The properties of nitrided steel. The time resolved diagnostics indicate that
improvement in wear resistance by plasma nitriding can be attributed to this could be associated with the lower discharge fluctuations and in­
the higher hardness of nitrided samples, particularly samples nitrided at stabilities at higher peak currents and higher electron temperatures.
a low pulsed duty cycle. It follows Archard's equation V = kW/H, where
V is the volume of the wear track, H is hardness, W is a normal load CRediT authorship contribution statement
applied to the sample, k is constant known as wear coefficient, and this
equation correlates the wear volume and hardness [51]. The wear rate in M. Naeem: Writing – original draft, Formal analysis, Conceptuali­
Fig. 12 and hardness in Fig. 9 agree with Archard's equation. The zation. Madiha Qadeer: Data curation, Formal analysis. Zaka-ul-islam
improvement in wear resistance by plasma nitriding can be ascribed to Mujahid: Data curation, Writing – review & editing, Resources. N.U.
improved hardness and to the diffusion of nitrogen atoms at the inter­ Rehman: Resources, Formal analysis. J.C. Díaz-Guillén: Resources,
stitial sites of the steel sample. The diffusion of nitrogen atom reduces Formal analysis. R.R.M. Sousa: Data curation, Writing – review &
the slipping probability of planes during the sliding motion of the ball editing. M. Shafiq: Data curation, Writing – review & editing,
against the sample, so wear resistance is improved [52]. The lowest wear Resources.
rate by plasma nitriding at 15 % duty cycle is due to excessive avail­
ability of nitrogen atoms and their diffusion at interstitial sites. Declaration of competing interest
The corrosion resistance of nitrided samples is compared with base
material using anodic polarization curves, as presented in Fig. 13. The The authors declare that they have no known competing financial
corrosion curves are shifted to higher potential and lower current den­ interests or personal relationships that could have appeared to influence
sities, showing improvement in samples' corrosion resistance after the work reported in this paper.
plasma nitriding. Specifically, when samples are nitrided at 15 %, the
curves move toward higher potential and lower current densities. Thus, Data availability
the best corrosion resistance is attained under this condition by
following the hardness and wear resistance. The corrosion performance Data will be made available on request.
is quantified by measuring corrosion rates, as presented in Fig. 14, which
shows the lowest corrosion rates for the sample treated at a low duty Acknowledgment
cycle. This improvement in corrosion resistance can be ascribed to the
presence of a protective layer over the base material, containing iron M. Naeem is thankful to Higher Education Commission of Pakistan
nitrides (Fe4 N, Fe3 N) [53]. The lowest corrosion rates of the sample for partial financial support, through HEC-NRPU Project No. 14417.
treated at a low duty cycle can be credited to the excessive presence of

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M. Naeem et al. Surface & Coatings Technology 464 (2023) 129542

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