Materials Research Express

PAPER

Novel synthesis of molybdenum nitride/oxide on AISI-316 steel assisted

with active screen plasma treatment
To cite this article: A B V Leitao et al 2019 Mater. Res. Express 6 116501

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IOP Publishing Mater. Res. Express 6 (2019) 116501 https://doi.org/10.1088/2053-1591/ab42e1

Materials Research Express

PAPER

Novel synthesis of molybdenum nitride/oxide on AISI-316 steel

RECEIVED
14 June 2019 assisted with active screen plasma treatment
REVISED
9 September 2019
ACCEPTED FOR PUBLICATION
A B V Leitao1, C L Lima2, B C Viana2, Barros Neto3, J A P Costa4, T H C Costa5, I A De Souza5,
27 August 2019 M Naeem6 and R R M Sousa1
1
PUBLISHED Mechanical Engineering Department, Federal University of Piaui, Brazil
19 September 2019 2
Department of Physics, Federal University of Piaui, Brazil
3
Materials Engineering Department, Federal University of Piaui, Brazil
4
Physics Department, State University of Rio Grande do Norte, Brazil
5
Mechanical Engineering Department, Federal University of Rio Grande do Norte, Brazil
6
Department of Physics, Women University of Azad Jammu and Kashmir, Bagh, Pakistan
E-mail: thercioc@ufrn.edu.br and mnaeem@phys.qau.edu.pk

Keywords: indentation and hardness, surfaces, plasma nitriding, oxidation, active screen plasma

Abstract
In this work, novel synthesis of molybdenum nitride/oxide coating on AISI-316 is attained by active
screen plasma (ASP) treatment, using molybdenum active screen (AS). Molybdenum nitride is
synthesized in N2-H2 environment, while oxidation is carried out in O2-H2 and O2-Ar
environment. The synthesized coatings are characterized by microhardness tester, X-ray diffraction
and scanning electron microscopy . The results show a successful synthesis of coating with improved
hardness. This study illustrates that using molybdenum active screen, molybdenum nitride/oxide
coating can be produced and industrial compatibility of this technique increases the effectiveness
of these results on wide-scale engineering applications.

1. Introduction

Among the transition metals, molybdenum is an important one, used as an alloying element for the enhancement
of wear resistance of stainless steels due to its excellent strength, high melting point as well as better stability at
higher temperature [1]. Furthermore, its nitrides and oxides are more valued in surface engineering applications
due to excellent hardness, better corrosion resistance, lower coefficient of friction and better solid lubrication
features [1]. Furthermore, such coatings are extensively used for lithium batteries, smart windows, display devices
and anti-dazzling coatings [2]. The Mo-based coatings can be deposited by numerous approaches such as filtered
cathodic arc [3], ion beam assisted deposition [4], nitridation of molybdenum films [5], dense plasma focus device
[6], plasma enhanced chemical vapor deposition [7], ion-implantation [8], cathodic arc PVD [3], DC and RF
magnetron sputtering [9], pulsed laser deposition [10] and atomic layer deposition [11]. Unfortunately, most of
these coatings exhibit certain shortcomings like limited coating thickness and higher energy consumption [1, 12].
Around two decades, active screen plasma treatment, an innovative advanced surface modification technique
for nitriding of various materials was introduced. Its working mechanism is based on the sputtering of active
screen material due to ions bombardment, subsequent deposition of reactant product (depending upon
processing gas, either nitrides or oxides) on the sample surface and lastly thermal diffusion of atomic species [13].
As, in this technique, besides the thermal diffusion, active screen material is also deposited on the sample, thus it
can be used for surface alloying with active screen material. In this sense, several authors used this technique for
surface alloying of various elements like silver, niobium, copper, aluminum and titanium [14–17].
Using this fact, here we attempted to synthesize Mo-based coatings such as molybdenum nitride and
molybdenum oxide using molybdenum active screen. The nitriding is carried out using well-known nitrogen-
hydrogen gasses admixture, while oxidizing is carried out using oxygen-hydrogen as well as oxygen-argon
mixture to attained best results. The synthesized coatings are verified from phase structure by X-ray diffraction
as well as Raman spectroscopy.

© 2019 IOP Publishing Ltd

IOP Publishing Mater. Res. Express 6 (2019) 116501 A B V Leitao et al

Figure 1. A cross-sectional view of the cathodic cage and spatial arrangement of the sample.

2. Experimental details

The mirror polished samples of AISI-316 cleaned with acetone were used in this study. The plasma treatment
was carried out in the active screen plasma reactor, as reported [18], whereas the schematic diagram of active
screen along with sample arrangement is shown in figure 1. The AS is made up of 3 mm thick molybdenum
with height 35 mm and diameter 45 mm. The gasses mixture was N2:H2 = 180:60 sccm (plasma nitriding),
whereas O2-H2 = 50:50 sccm and O2-Ar = 20:80 sccm (plasma oxidation), which were optimized prior to this
experiment. The processing temperature was 400 °C, time 5 h, pressure 1.5 torr and processing power ~ 1 kW.
The processing temperature was measured using thermocouple placed under the sample holder. As the
temperature is dependent on gasses admixture, in order to keep temperature as fixed parameter, it was
maintained using external heater placed below sample holder. The processing power was provided by pulsed
source obtained from the SDS PUL 600/08 company which uses a rectifying system that receives voltage
from the conventional mains (alternating current 220 V) and converts in to pulsed current. This voltage source
has a pulsed output AC / DC converter with a voltage peak of 600 Vand output current up to 8 A. The hardness,
phase structure and surface/cross-sectional morphology was analyzed by Vickers hardness tester with a load
of 50 gf, X-ray diffraction (CuKα-radiation source) and scanning electron microscopy, respectively, whose
details can be found in our previous articles [16, 19, 20].

3. Results and discussion

The hardness profile of base material, nitrided and oxidized samples is plotted in figure 2 and the
corresponding phase structure is plotted in figure 3. It reveals improvement in hardness after plasma

Figure 2. Surface hardness of nitrided and oxidized samples.

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IOP Publishing Mater. Res. Express 6 (2019) 116501 A B V Leitao et al

Figure 3. X-ray diffraction of nitrided and oxidized samples.

processing, and in particular, the hardness of sample oxidized in a nitrogen-hydrogen environment is highest
(1152 HV), which is more than 6 times base material (187 HV). This difference in hardness with the change in
processing environment can be clarified by the X-ray diffraction pattern. The base material demonstrates the
well-known austenite phase (not shown here), which is the expected phase of AISI-316 steel, which have a face-
centered cubic structure. The plasma nitrided sample (PN;N2-H2) shows the occurrence of molybdenum
nitride phases (MoN, Mo2N0.76JCPDS 03-1181 and 65-6236), whereas no iron-containing phases are detected.
It can be attributed to the significantly higher amount of sputtered molybdenum from the active screen and a
considerable amount of nitrogen species in the plasma environment. The absence of iron-containing phases
indicates the development of thick modified layer. The plasma oxidized sample (PO;O2-H2) shows the
occurrence of molybdenum trioxide (MoO3JCPDS 35-0609), which usually exhibits an orthorhombic crystal
structure. On the other hand, PO (O2-Ar) sample depicts the presence of molybdenum dioxide (MoO2JCPDS
32-0671) and trioxide (MoO3JCPDS 35-0609). Thus, it indicates a significant influence of processing
environment on the phase structure due to change in plasma reactivity. This can be ascribed as: in O2-H2
mixture discharge, hydrogen has small collisional cross-section over oxygen, thus the generation of oxygen
atomic species due to electron impact dissociation increases (due to high electron temperature and thus
electron impact dissociation). On the other hand in O2-Ar mixture, Penning dissociation due to argon
metastable states contributes in dissociation [21]. However, as electron impact dissociation mechanism is
dominant, thus it is expected O2-H2 admixture is more suitable due to high production of oxygenatomic
species. Furthermore, argon gas is not economically feasible (although gases cost is not a critical issue for
laboratory scale reactor as used in this study, however, for industrial scale reactors, it plays significant role),
thus O2-H2 is more preferable for plasma oxidation. Due to similar reason, as we reported earlier the influence
the of both argon and hydrogen addition in nitrogen discharge on nitriding performance, we used only
hydrogen admixed nitrogen discharge for plasma nitriding, rather than argon admixture [22].
To analyze surface appearance and thickness of the modified layer, SEM results are presented in figure 4.
It shows the uniform surface appearance under all processing condition, which is the novelty of ASP treatment
technique [23]. The thickness of the modified layer is of the order of 5 μm for PN(N2-H2) and PO(O2-H2)
treated sample, and 3 μm for PO(O2-Ar) sample. It also supports the fact that hydrogen admixing is more
efficient over argon for both nitriding and oxidation.
The ASP treatment used in the current study is an efficient technique to attain sufficient thickness, and thus
it has a lower processing cost. Moreover, the nitriding/oxidation as well as alloying with molybdenum is

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IOP Publishing Mater. Res. Express 6 (2019) 116501 A B V Leitao et al

Figure 4. SEM and cross-sectional images of (a) PN, (b) PO (O2-H2) and (c) PO (O2-Ar).

attained in a single processing unit in a single step treatment, with lower treatment temperature and treatment
time, and thus this study is more valuable. Interestingly, ASP treatment is compatible with the industry,
thus results attained from this study are expected to be appreciated on industrial scale applications.

4. Conclusion

This study reports the synthesis of molybdenum nitride/oxide coating in a novel way by active screen plasma
treatment. It is found that hydrogen addition in nitrogen and oxygen gas is suitable for nitriding and oxidizing.
The results depict the development of excellent film quality, with enhanced surface hardness, and MoN and
MoO3 as a leading phase in nitriding and oxidizing process, respectively. The current system is industrially
well-matched [24]; it uses low processing temperature, comparatively small processing time, it uses singe setup
and single step treatment for nitriding/oxidizing as well as molybdenum alloying, thus it can be used as
effective surface engineering treatment. This work reports the successful synthesis of this coating by using novel
technique of ASP, however, the comprehensive analysis of such coating on wear, corrosion and nanohardness
will be reported in future.

Acknowledgements
This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior—Brasil
(CAPES)—Finance Code 001, To whom we thank for the financial support.

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