Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Microstructural evaluation of gas nitrided AISI 316 LN austenitic

stainless steel
M. Arun Prasad ⇑, G. Dharmalingam, Sachin Salunkhe
Department of Mechanical Engineering, Vel Tech Rangarajan Dr. Sagunthala R&D Institute of Science and Technology, Avadi, Chennai, India

a r t i c l e i n f o a b s t r a c t

Article history: Direct utilization of austenitic stainless steel is limited in numerous industries due to its low surface
Available online xxxx hardness. To improve the hardness of steels, gas nitriding is a convenient technique to enhance the sur-
face hardness of austenitic stainless steel (316 LN). AISI 316 LN austenitic grade stainless steel were uti-
Keywords: lized for various applications like nuclear cladding tubes, heaters, turbine parts and blower parts.
Austenitic stainless steel Nitiriding was carried out for three different hours namely 14, 24 and 72 hrs for the austenitic stainless
Gas nitiriding in the current study. A maximum surface hardness of 1200 HV is obtained for gas nitirding technique
XRD analysis
when compared to 210 HV for the untreated specimen. Gas nitrided specimen shows a uniform nitride
Vickers’s hardness
layer on the 316 LN stainless steel. Similarly XRD analysis of the nitrided specimen unveil the distribution
of iron nitride phase which occurred during nitriding process. An effective case depth of the compounded
layer from gas nitriding was found to be 30.7 lm.
Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 4th International
Conference on Advances in Mechanical Engineering (ICAME 2022).

1. Introduction observed in chrome plated steels [8,9]. The presence of these micro
cracks will lead to crack initiation and propagation cites which lim-
High amount of chromium present in austenitic stainless steel its the life of coating on steels.
forms a protective layer of chromium oxide film over the surface. A potential alternative for chrome plated steels working at ele-
This film resists corrosive environment as well as enhances the vated temperatures is nitriding technique. During the nitriding
performance of steel in vacuum conditions [1,2]. Generally, auste- process the formation of nitride microstructure as a result of diffu-
nitic stainless steels are widely used in engineering applications sion will have better stress accommodation within the steel
due to its better corrosion and oxidation resistance along with matrix. The thermal expansion co-efficient of chromium is
superior mechanical strength [3,4]. Strengthening of stainless steel between chromium nitride and austenitic stainless steel. The pres-
has drawn much attention in the past decade through various ence of untreated sample which is between the metal matrix and
approaches by varying its chemical compositions mainly through nitrided layer enhances the bonding strength during thermal stres-
solid solution strengthening and grain refrainment [5–7]. For sev- ses. When compared to chrome plated steels nitrided sample con-
eral applications namely automotive, aerospace, nuclear and other sists of improved room and high temperature properties along
sectors of engineering uses plating of stainless steel using hard with corrosion resistance in acidic environment [10,11].
chrome for hardening its surface. Room temperature hardness of Gas nitriding is a well-known technique for surface improvisa-
chrome plated steel exhibit hardness values around 800–1100 tion in steel components [12]. When compared to plasma nitriding
VHN but suffers from hot hardness phenomenon. Moreover, the which is a popular technique, gas nitriding is less expensive. Pres-
hardness values exhibited at room temperatures deteriorated ence of chromium in austenitic stainless steel has a high affinity to
when exposed to high temperatures even for short durations. oxygen which results in the formation of chromium oxide layer.
Due to this constraint steel plated with chrome were restricted This oxide layer acts as a barrier for diffusion which transports
for high temperature application. Similarly, micro cracks were also nitrogen in stainless steel. Therefore, reduction of oxide layer is
essential for nitriding process. To get higher case depths higher
nitriding temperatures are required for reasonable time period.
⇑ Corresponding author. Similarly, appropriate process parameters are essential for
E-mail address: [email protected] (M. Arun Prasad).

https://doi.org/10.1016/j.matpr.2022.08.060
2214-7853/Copyright Ó 2022 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the 4th International Conference on Advances in Mechanical Engineering (ICAME 2022).

Please cite this article as: M. Arun Prasad, G. Dharmalingam and S. Salunkhe, Microstructural evaluation of gas nitrided AISI 316 LN austenitic stainless
steel, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2022.08.060
M. Arun Prasad, G. Dharmalingam and S. Salunkhe Materials Today: Proceedings xxx (xxxx) xxx

nitriding which helps in eliminating the formation of sensitization longer time two stage gas nitriding was carried out where the first
of steel. Further the nitride layer inhibits the diffusion kinetics of stage was at 510 °C for 24 hrs and stage two at 535 °C for 48 hrs.
nitriding. Optical images were observed for the samples to check the case
The current study aims to evaluate the processing time of gas depth of nitriding. To reveal the microstructure the samples were
nitriding by validating the case depth using microstructural evalu- chemically etched using a combination of 20 ml HCL, 20 ml
ation, X-ray diffraction in austenitic stainless steel (316 LN). HNO3, 20 ml acetic acid and 4 ml of glycerol. The different phases
present during nitriding were determined using X-ray diffraction
technique with CuK alpha radiation. Hardness of the nitrided sam-
2. Experimental procedures
ples were measured using Vickers hardness tester by applying a
load of 10kgf with a dwell time of 15 sec using diamond intender.
Austenitic stainless steel of 316 LN grade were cut as per the
dimension of 30x20x5 mm through wire cut EDM process as per
ASTM A355 [13]. All the specimens were punched for identifica-
tion. Before the samples went for nitriding process all the samples 3. Results and discussion
were de-greased in a de-greasing tank by cleaning the surface of
the samples with trichloro ethylene. Even though de-greasing the Fig. 1 shows, the optical micrograph of 316 LN austenitic stain-
surface of the sample removes the presence of dirt and oil, but less steel for different nitriding hours. Fig. 1(a) shows, the optical
the removal of oxide layer due to the presence of chromium and micrograph of 316 LN austenitic stainless steel. Fig. 2 (b-d) repre-
iron will not be facilitated. Reduction of the oxide layer was accom- sents the optical micrograph of gas nitrided samples for 14hrs,
plished in the furnace during pre-heating of the samples at 350 °C 20hrs and 72hrs respectively. For Fig. 2 (b & c) as the nitriding
before nitirding process by means of halogen based reducing agent hours increases from 14hrs to 20hrs the case depth also increases
which will be kept at the bottom of the furnace. Gas nitriding was from 29.6 lm to 30.7 lm. It also shows that the diffusion rate is
carried out using pure ammonia gas at a constant rate of 100 ml/ propotional to the time period during nitriding [14,15]. It can also
min. The temperature at which nitriding was carried out at 550 be understood that the nitride layer formed is strong, thick and has
°C for a time period of 14, 20 and 72 hrs respectively for two sam- a uniform layer from the micrograph. But as the nitriding hours are
ples. The samples were named subsequently as GN1, GN2 and GN3 too long the resulting case depth decreases when compared to the
respectively. To check the diffusivity of gas nitiriding process for case depth obtained for 14hrs and 20hrs. It can be attributed to the

Fig. 1. Optical micrograph of 316 LN austenitic stainless steel (a) untreated specimen, (b) GN1 specimen, (c) GN2 specimen and (d) GN3 specimen.

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M. Arun Prasad, G. Dharmalingam and S. Salunkhe Materials Today: Proceedings xxx (xxxx) xxx

Fig. 2. X-ray diffraction of 316 LN austenitic stainless steel (a) untreated specimen, (b) GN1 specimen, (c) GN2 specimen and (d) GN3 specimen.

fact that as the time increases reduction in nitrogen gas took place due to the phase transformation near the surface of the samples
during nitriding process at lower eutectoid temperatures [14]. which is confirmed through XRD analysis.
Fig. 2(a) represents the X-ray Diffraction (XRD) analysis of 316
LN austenitic stainless steel, whereas Fig. 2(b), Fig. 2(c) and Fig. 2 3.1. Microhardness evaluation
(d) consists of XRD analysis of gas nitrided specimen. It is evident
from the diffraction patterns that different phases of nitrides were Micro hardness measurements were carried out using Vickers
formed namely Fe3N, Fe4N and expanded austenite phases within hardness measurement to evaluate the influence of nitriding on
the samples. From Fig. 2(a) shows, the diffraction pattern of the samples. Hardness measurement were taken for all the sam-
retained austenite for 316 LN austenitic stainless steel. For GN1 ples at the nitrided surface and tabulated in Table 1. It can be seen
sample which was gas nitrided for 14hrs shows the presence of that the hardness values of the nitrided layer is much higher when
iron nitrides in the form of Fe3N at different diffraction angles compared to that of the base material. The percentage of increase
which shows the formation of nitrided layers along the 316 LN aus- in hardness value is approximately about 400–500 %. Due to the
tenitic stainless steel. Moreover the increase in nitriding time gives presence of different nitrides present in the surface of the treated
rise to the formation of complex Fe4N peaks during XRD analysis sample the hardness value increases. Maximum hardness of 1200
for GN2 samples which was nitrided for 24hrs. When compared Hv for GN2 sample is attributed to the optimum formation of iron
to GN1 samples the formation of complex Fe4N dominated the nitrides which is similar to the study conducted by Ralf Eich [16].
Fe3N phase. This is due to increase in nitriding time led to the for- As the time taken for the nitriding of GN3 sample prolonged to
mation of Fe4N phase. Overall from the XRD analysis it can be 72hrs when compared to other samples indicates the supersatura-
found out that the shift and broadening of c-FeN peaks to lower tion reaction which took place at the grain boundaries. This
angles when compared to austenitic peaks from Fig. 2(a). The shift- resulted in low hardness value of the specimen. Even though from
ing of peaks indicates the formation of residual stresses induced XRD results of 2(d) shows the formation of Fe3N but was not able
due to the nitrided layer. Moreover the lattice expansion also led
to the shift of peaks to lower 2h values. This shows that nitrogen
supersaturation led to the shifting and broadening of peaks during Table 1
the formation of iron-nitrides. Dissolution of nitrides into the Hardness values of the nitrided 316 LN austenitic stainless steel.

metal matrix and formation of nitrides in different proportion let Sl No. Sample Name Hardness (Hv)
to the formation of microstrain within the nitrided samples. 1 Untreated 230 ± 10
Another reason for the broadening of peaks may be attributed to 2 GN1 1059 ± 10
the overlapping of Fe3N and Fe4N peaks with the austenite peaks. 3 GN2 1200 ± 10
The change in sample appearance from optical micrographs is 4 GN3 856 ± 10

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M. Arun Prasad, G. Dharmalingam and S. Salunkhe Materials Today: Proceedings xxx (xxxx) xxx

to form complex iron nitride (Fe4N) phase. Near the surface area Declaration of Competing Interest
the rate of diffusion of nitrogen is very high. As the depth of diffu-
sion increases rate of nitrogen diffusion decreases. In stainless The authors declare that they have no known competing finan-
steels hardness values decreases due to sensitization reaction. cial interests or personal relationships that could have appeared
But in the case of 316 LN the amount of carbon is very low and to influence the work reported in this paper.
the phenomenon of sensitization is negligibly small. Unstable
nitride formation is one of the main reason for the decrease in
hardness of GN3 sample. References

[1] A. Smith, Influence of environment on the unlubricated wear of 316 stainless

4. Conclusions steel at room temperature, Tribol. Int. 19 (1) (1986) 3–10.
[2] A. Smith, The unlubricated reciprocating sliding wear of a martensitic stainless
steel in air and CO2 between 20 and 300° C, Wear 123 (3) (1988) 313–331.
The process of nitriding is one of the technique to improve the [3] M. Arun Prasad, E. Pavithra, G. Dharmalingam, D. Siva Prakasham,
surface properties of austenitic stainless steel. In the present study Characterisation and structural transformation of yttria dispersed austenitic
investigation of gas nitriding on 316 LN austenitic stainless steel is steel through VHP, Mater. Sci. Technol. 37 (13) (2021) 1139–1151.
[4] G. Dharmalingam, P. Sellamuthu, M.A. Prasad, Prediction of mechanical
carried out and the following conclusion were reached. properties for ferritic ODS steel using the nanoindentation test, in: AIP
Conference Proceedings. AIP Publishing LLC, 2021.
 During gas nitriding a uniform thick nitrided layer was formed [5] G. Dharmalingam, M.A. Prasad, S. Salunkhe, Optimization of milling speed and
time in mechanical alloying of ferritic ODS steel through taguchi technique,
for the specimen GN1 and GN2 with case depth of 29.6 lm and Int. J. Simul. Multi. Des. Optim. 12 (2021) 25.
30.7 lm respectively. GN3 showed lesser case depth of 10.4 lm [6] G. Dharmalingam, S. Prabhukumar, M. Arun Prasad, Synthesis and
which can attributed to the fact that as nitriding time increases Characterization of 17 Cr Ferritic ODS Steel Developed Through Vacuum Hot
Pressing, in: Innovative Design, Analysis and Development Practices in
reduction in nitrogen gas diffusion at lower eutectoid Aerospace and Automotive Engineering, Springer, 2021, pp. 285–294.
temperatures. [7] M. Arun Prasad, E. Pavithra, Vacuum Hot Pressed Novel 21–4N Valve Steel
 Formation of iron-nitrides were observed during XRD analysis. Strengthened by Y-Ti-O Through High-Energy Ball Milling, J. Mater. Eng.
Perform. 29 (12) (2020) 8080–8092.
Due to the residual stresses induced due to nitriding peaks
[8] K.-L. Lin, C.-J. Hsu, I.-M. Hsu, J.-T. Chang, Electroplating of Ni-Cr on steel with
shifts and broadening of peaks were clearly visible from the pulse plating, J. Mater. Eng. Perform. 1 (3) (1992) 359–361.
XRD analysis. [9] L. Wang, K. Nam, S. Kwon, Effect of plasma nitriding of electroplated chromium
 Hardness value of the nitriding sample shows superior hardness coatings on the corrosion protection C45 mild steel, Surf. Coat. Technol. 202 (2)
(2007) 203–207.
when compared to untreated 316 LN austenitic stainless steel. [10] M. Taguchi, J. Kurihara, Effect of surface nitriding on corrosion resistance of
Maximum hardness of 1200 Hv for GN2 sample is attributed chromium in sulfuric acid solution, Mater. Trans., JIM 32 (12) (1991) 1170–
to the optimum formation of iron nitrides. Supersaturation hap- 1176.
[11] M. Van Stappen, L.M. Stals, M. Kerkhofs, C. Quaeyhaegens, State of the art for
pens due to prolonged nitriding time which results in decrease the industrial use of ceramic PVD coatings, Surf. Coat. Technol. 74-75 (1995)
in hardness of GN3 sample. 629–633.
[12] M.J. Baldwin, M.P. Fewell, S.C. Haydon, S. Kumar, G.A. Collins, K.T. Short, J.
Tendys, Rf-plasma nitriding of stainless steel, Surf. Coat. Technol. 98 (1-3)
CRediT authorship contribution statement (1998) 1187–1191.
[13] N. Chen, Y. Chen, J. Ai, J. Ren, R. Zhu, X. Ma, J. Han, Q. Ma, Automatic detection
M. Arun Prasad: Conceptualization, Methodology, Formal anal- of pearlite spheroidization grade of steel using optical metallography, Microsc.
Microanal. 22 (1) (2016) 208–218.
ysis, Data curation, Writing – original draft. G. Dharmalingam: [14] K.A. Widi et al., White Layer Control on AISI 316L Using Temperature and Gas
Methodology, Formal analysis, Writing – review & editing. Sachin Nitriding Diffusion Stage Process, Int. Rev. Mech. Eng. (I. RE. ME) 11 (8) (2017)
Salunkhe: Writing – review & editing, Supervision. 613–618.
[15] D.Q. Peng, T.H. Kim, J.H. Chung, J.K. Park, Development of nitride-layer of AISI
304 austenitic stainless steel during high-temperature ammonia gas-nitriding,
Data availability Appl. Surf. Sci. 256 (24) (2010) 7522–7529.
[16] R.E. Schacherl, Growth kinetics and microstructure of gaseous nitrided iron
chromium alloys, 2004.
Data will be made available on request.