Effect of Nitriding Time on the Structural Evolution and Properties of Austenitic Stainless Steel Nitrided Using High Power Pulsed DC Glow Discharge Ar/N2 Plasma


  • S. Yang Teer Coatings Ltd., Miba Coating Group,
  • M. Kitchen Materials and Engineering Research Institute, Sheffield Hallam University
  • Q. Luo Materials and Engineering Research Institute, Sheffield Hallam University
  • D.N. Ievlev Teer Coatings Ltd., Miba Coating Group,
  • K.E. Cooke Teer Coatings Ltd., Miba Coating Group,




Pulsed Glow Discharge Plasma, Nitriding, Austenitic Stainless Steel, Structural Characterization, Tribological Properties.


A high power pulsed DC glow discharge plasma (HPPGDP) system was employed to perform fast nitriding of AISI 316 austenitic stainless steel in Ar and N2 atmosphere. In-situ optical emission spectroscopy and Infrared pyrometer measurements were used during the plasma nitriding to investigate the effect of dynamic plasma on the nitriding behaviour. SEM and EDX, XRD, Knoop indentation, and tribo-tests were used to characterise microstructures and properties of the nitrided austenitic stainless steel samples. HPPGDP produced high ionization of both Ar and N2 in the plasma that corresponded to dense ion bombardment on the biased steel samples to induce effective plasma surface heating and to form high nitrogen concentration on the biased steel surfaces, and therefore fast nitriding (> 10µm/hour) was achieved. Various phases were identified on the nitrided stainless steel samples formed from a predominantly a single phase of nitrogen supersaturated austenite to a multi-phase structure comprising chromium nitride, iron nitride and ferrite dependent on the nitriding time. All the nitrided AISI 316 austenitic stainless steel samples were evaluated with high hardness (up to 17.3 GPa) and exceptional sliding wear resistance against hardened steel balls and tungsten carbide balls.


[1] Llewellyn IP, Rimmer N, Scarsbrook GA, Heinecke RA. Low temperature pulsed plasma deposition: III. A method for the deposition of aluminium and tin at room temperature. Thin Solid Films 1990; 191: 135-145.
[2] Yukimura K, Mieda R, Tamagakin H, Okimoto T. Electrical characteristics of arc-free high-power pulsed sputtering glow plasma. Surface and Coatings Technology 2008; 202: 5246-5250.
[3] Guiberteau E, Bonhomme G, Hugon R, Henrion G. Modelling the pulsed glow discharge of a nitriding reactor. Surface and Coatings Technology 1997; 97: 552-556.
[4] Rosales I, Martinez H, Ponce D, Ruiz JA. Wear performance of Nb-alloyed, pulsed plasma nitrided Mo3Si intermetallic. International Journal of Refractory Metals and Hard Materials 2007; 25: 250-255.
[5] Grün R. Combination of different plasma assisted processes with pulsed d.c.: cleaning, nitriding and hardcoatings. Surface and Coatings Technology 1995; 74-75: 598-603.
[6] Novák P, Vojt?ch D, Šerák J, Knotek V, Bártová B. Duplex surface treatment of the Nb-alloyed PM tool steel. Surf Coat Technol 2006; 201: 3342-3349.
[7] Blawert C, Mordike BL, Huchel U, Strämke S, Collins GA, Short KT, Tendys J. Surface treatment of nitriding steel 34CrAlNi7: a comparison between pulsed plasma nitriding and plasma immersion ion implantation. Surface and Coatings Technology 1998; 98: 1181-1186.
[8] Rauschenbach B. Encyclopedia of Materials: Science and Technology 2001; 7023-7027.
[9] Heintz MJ, Hieftje GM. Langmuir-probe measurements of a pulsed and steady-state rf glow-discharge source and of an rf planar-magnetron source Spectrochimica Acta Part B: Atomic Spectroscopy 1996; 51: 1629-1646.
[10] Bogaerts A, Neyts E, Gijbels R, van der Mullen J. Gas discharge plasmas and their applications. Spectrochimica Acta Part B: Atomic Spectroscopy 2002; 57: 609-658.
[11] Schonjihn C, Donohue LA, Lewis DB, Munz WD, Twesten RD, Petrov I. Enhanced adhesion through local epitaxy of transition-metal nitride coatings on ferritic steel promoted by metal ion etching in a combined cathodic arc/unbalanced magnetron deposition system. J Vac Sci Technol 2000; 18: 1718-1723.
[12] Schonjihn C, Paritong H, Munz WD, Twesten RD, Petrov I. Influence of the interface composition on the corrosion behaviour of unbalanced magnetron grown niobium coatings on steel. J Vac SciTechnol 2001; 19: 1392-1398.
[13] Hultman L, Munz WD, Musil J, Kadlec S, Petrov I, Greene JE. Low-energy (-100 eV) ion irradiation during growth of TiN deposited by reactive magnetron sputtering - Effects of ion flux on film microstructure. J Vac Sci Technol 1991; 9: 434-438.
[14] Kersten H, Deutsch H, Steffen H, Kroesen GMW, Hippler R. The energy balance at substrate surfaces during plasma processing. Vacuum 2001; 63: 385-431.
[15] Akamatsu H, Yatsuzuka M. Simulation of surface temperature of metals irradiated by intense pulsed electron, ion and laser beams. Surf Coat Technol 2003; 169: 219-222.
[16] Galvao NKAM, Costa BLS, Mendes MWD, de Brito RA, Souza CF, Alves C. Structural modifications of M35 steel submitted to thermal gr-adients in plasma reactor. J Mater Proc Technol 2008; 200: 115-119.
[17] Lundin D, Stahl M, Kersten H, Helmersson U. Energy flux measurements in high power impulse magnetron sputtering. L Phys D – Appl Phys 2009; 42: 185202.
[18] Lo KH, Shek CH, Lai JKL. Recent developments in stainless steels. Mater Sci Eng 2009; R65: 39-104.
[19] Buhagiar J, Bell T, Sammons R, Dong HS. Evaluation of the biocompatibility of S-phase layers on medical grade austenitic stainless steels. J Mater Sci – Mater Med 2011; 22: 1268-1278.
[20] Bordjih K, Jouzeau EY, Mainard D, Payan E, Delagoutte JP, Netter P. Evaluation of the effect of three surface treatments on the biocompatibility of 316L stainless steel using human differentiated cells. Biomaterials 1996; 17: 491-500.
[21] Gavriljuk VG, Shanina BD, Berns H. ON the correlation between electron structure and short range atomic order in iron-based alloys. Acta Mater 2000; 48: 3879-3893.
[22] Lei MK, Zhu XM. Chemical state of nitrogen in a high nitrogen face-centred-cubic phase formed on plasma source ion nitride austenitic stainless steel. J Vac Sci Technol 2004; 22: 2067-2070.
[23] Moslemzadeh N, Beamson G, Diplas S, Tsakiropoulos P, Watts JF. Monitoring atomic level electronic changes in the alloying of stainless steels with Auger and photoelectron spectroscopy. Surf Sci 2008; 602: 216-225.
[24] Diplas S, Moslemzadeh N, Watts JF, Beamson G, Tsakiropoulos P. An XPS study of the interatomic charge distribution in stainless steels. Surface and Interface Analysis 2010; 42: 722-725.
[25] Parascandola S, Moller W, Willaimson DL. The nitrogen transport in austenitic stainless steel at moderate temperature. Appl Phys Lett 2000; 76: 2194-2196.
[26] Moller W, Parascandola S, Telbizoiva T, Gunzel R, Richter E. Surface processes and diffusion mechanisms of ion nitriding of stainless steel and aluminium. Surf Coat Technol 2001; 136: 73-79.
[27] Moskalioviene T, Galdikas A, Riviere JP, Pichon L. Modeling of nitrogen penetration in polycrystalline AISI 316L austenitic stainless steel during plasma nitriding. Surf Coat Technol 2011; 205: 3301-3306.
[28] Lei MK. Phase transformation in plasma source ion nitride austenitic stainless steel at low temperature. J Mater Sci 1999; 34: 5975-5982.
[29] Li GJ, Peng Q, Li C, Wang Y, Gao J, Chen SY, Wang J, Shen BL. Effect of DC plasma nitriding temperature on microstructure and dry-sliding wear properties of 316L stainless steel. Surf Coat Technol 2008; 202: 2749-2754.
[30] Martinavicius A, Abrasonis G, Scheinost AC, Danoix R, Danoix F, Stinville JC, Talut G, Templier C, Liedke O, Gemming S, Moller W. Nitrogen interstitial diffusion induced decomposition in AISI 304L austenitic stainless steel. Acta Mater 2012; 60: 4065-4076.
[31] Zhang ZL, Bell T. Structure and corrosion resistance of plasma nitride stainless steel. Surf Eng 1985; 1: 131-136.
[32] Ichii K, Fujimura K, Takase T. Structure of the on-nitrided layer of 18-8 stainless steel. Technical Report Kansai University 1986; 27: 135-144.
[33] Dong H. S-phase surface engineering of Fe-Cr, Co-Cr and Ni-Cr alloys. Int Mater Rev 2010; 55: 65-98.
[34] Yang S, Cooke K, Sun H, Li X, Lin K, Dong H. Development of advanced duplex surface systems by combining CrAlN multilayer coatings with plasma nitrided steel substrates. Surf Coat Technol 2013; 236: 2-7.
[35] Petitjean L, Ricard A. Emission spectroscopy study of N2-H2 glow discharge for metal surface nitriding. J Physics D: Appl Phys 1984; 17: 919-929.
[36] Baravian G, Sultan G, Damond E, Detour H, Hayaud C, Jacquot P. Optical emission spectroscopy of active species in a TiCN PVD arc discharge. Surf Coat Technol 1995; 76-77: 687-693.
[37] Debal F, Wautelet M, Dauchot JP, Hecq M. Spectroscopic optical emission tomography of direct-current magnetron sputtering discharges in argon–nitrogen gas mixtures. Surf Coat Technol 1999; 116-119: 927-932.
[38] Luo Q, Yang S, Cooke KE. Hybrid HIPIMS and DC magnetron sputtering deposition of TiN coatings: deposition rate, structure and tribological properties. Surf Coat Technol 2013; 236: 13-21.
[39] Luo Q, Chi K, Li S, Barnard P. Microstructural Stability and Lattice Misfit Characteri-sations of Nimonic 263, Proceedings of the ASME 2012 Pressure Vessels & Piping Di-vision Conference (PVP2012), 2012; 6(Pts A & B): 197-206.
[40] Yang S, Li X, Renevier NM, Teer DG. Tribological properties and wear mechanism of sputtered C/Cr coating. Surf Coat Technol 2001; 142-144: 85-93.
[41] [NIST] NIST Atomic Spectra Database: http://www.nist.gov/pml/data/ asd.cfm
[42] Yilba? BS, ?ahinAZ,Al-Garni AZ, Said SAM, Ahmed Z, Abdulaleem BJ, Sami M. Plasma nitriding of Ti?6Al?4V alloy to improve some tribological properties. Surf Coat Technol 1996; 80: 287-292.
[43] Samandi M, Hedden BA, Smith DI, Collins GA, Hutchings R, Tendys J. Microstructure, corrosion and tribological behaviour of plasma immersion ion-implanted austenitic stainless steel. Surf Coat Technol 1993; 59: 261-266.
[44] Menthe E, Rie KT, Schultze JW, Simson S. Optical emission spectroscopy of active species in a TiCN PVD arc discharge. Surf Coat Technol 1995; 76-77: 687-693.
[45] Jackson GP, King FL. Probing excitation/ionization processes in millisecond-pulsed glow discharges in argon through the addition of nitrogen. Spectrochimica B 2003; 58: 185-209.
[46] Yasumaru N. Low-temperature ion nitriding of austenitic stainless steels. Mater Trans JIM 1998; 39: 1046-1052.
[47] Pedraza F, Grosseau-Poussard JL, Abrasonis G, Riviere JP, Dinhut JF. Influence of low energy high fluc nitrogen implantation on the oxidation behaviour of AISI 304L austenitic stainless steel. A Plly Phys 2003; 94: 7509-7520.
[48] Stinville JC, Villechaise P, Templier C, Riviere JP, Drouet M. Plasma nitriding of 316L austenitic stainless steel: Experimental investigation of fatigue life and surface evolution. Surf Coat Technol 2010; 204: 1947-1951.
[49] Sun Y, Li XY, Bell T. X-ray diffraction characterization of low temperature plasma nitride austenitic stainless steels. J Mater Sci 1999; 34: 4793-4802.
[50] Asgari M, Barnoush A, Johnsen R, Hoel R. Microstructural characterization of pulsed plasma nitrided 316L stainless steel. Mater Sci Eng 2011; 529A: 425-434.
[51] Wu D, Kahn H, Dalton JC, Michal GM, Ernst F, Heuer AH. Orientation dependence of nitrogen supersaturation in austenitic stainless steel during low-temperature gas phase nitriding. Acta Mater 2014; 79: 339-350.
[52] Münz WD, Donohue LA, Hovsepian PE. Properties of various large scale frbricatedTiAlN- and CrN-based superlattice coatings grown by combined cathodic arc-unbalanced magnetron sputter deposition. Surf Coat Technol 2000; 125; 269-277.
[53] Luo Q, Rainforth WM, Münz WD. Wear mechanisms of monolithic and multicomponent nitride coatings grown by combined arc etching and unbalanced magnetron sputtering. Surf Coat Technol 2001; 146-147: 430-435.
[54] Qu J, Blau PJ, Jolly BC. Tribological properties of stainless steels treated by colossal carbon supersaturation. Wear 2007; 263: 719-726.
[55] Li GY, Wang ZY, Lei MK. Transition of wear mechanisms of plasma spurce nitride AISI 316 austenitic stainless steel against cderamiccounterface. J Tribology – Transactions of The ASME 2012; 134: 011601.
[56] Luo Q. Origin of friction in running-in sliding wear of nitride coatings. Tribo Letters 2010; 37: 529-539.
[57] Sun Y, Bell T. Sliding wear characteristics of low temperature plasma nitrided 316 austenitic stainless steel. Wear 1998; 218: 34-42.
[58] Li Y, Wang Z, Wang L. Surface properties of nitrided layer on AISI 316L austenitic stainless steel produced by high temperature plasma nitriding in short time. Applied Surface Science 2014; 298: 243-250.




How to Cite

Yang, S., Kitchen, M., Luo, Q., Ievlev, D., & Cooke, K. (2016). Effect of Nitriding Time on the Structural Evolution and Properties of Austenitic Stainless Steel Nitrided Using High Power Pulsed DC Glow Discharge Ar/N2 Plasma. Journal of Coating Science and Technology, 3(2), 62–74. https://doi.org/10.6000/2369-3355.2016.03.02.3