Corujeira Gallo 09 PH D

ACTIVE SCREEN PLASMA SURFACE ENGINEERING OF AUSTENITIC STAINLESS STEEL
FOR ENCHANCED TRIBOLOGICAL AND CORROSION PROPERTIES
by SANTIAGO CORUJEIRA GALLO
A thesis submitted to
The University of Birmingham
for the degree of
DOCTOR OF PHILOSOPHY
School of Metallurgy and Materials
College of Engineering and Physical Sciences
The University of Birmingham
January 2009
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Abstract
Low temperature plasma surface engineering has proved to be a useful method for increasing the
hardness and wear resistance of austenitic stainless steel without reducing the corrosion resistance of
this alloy. Plasma carburising is of particular interest as it produces a thicker hardened layer than
plasma nitriding, and an equivalent improvement in the tribological and corrosion performance of the
base material.
In this project, the novel active screen (AS) plasma technique was used to carburise austenitic stainless
steel AISI 316. The layers of carbon expanded austenite obtained after active screen treatments were
compared with the one produced by conventional direct current (DC) plasma treatments. The hardening
and wear resistance produced by AS and DC plasma carburising were equivalent. With regard to
corrosion, the AS treated material performed better than its DC counterpart as a consequence of the
improved surface quality achieved with the former.
The mechanism of AS carburising was comparatively studied with its AS nitriding counterpart. Different
experimental arrangements and two plasma diagnostic techniques were used for this purpose: optical
emission spectroscopy and electrostatic probes. The evidence shows that AS nitriding relies on the
deposition of iron nitrides and the active species in the plasma to produce hardening, whilst AS
carburising relies on plasma activation and moderate ion bombardment.
Finally, the working principles of AS plasma furnaces are discussed with regard to the generation of
additional charged particles and their electrostatic confinement.

Acknowledgements
In first place, I would like to express my gratitude to Prof. T. Bell and Dr. H. Dong for giving me the
chance to develop this project in the Surface Engineering Group. I also want to thank Dr. E. Forlerer,
from Comisión Nacional de Energía Atómica (CNEA-CAC), for her continuous assistance and
encouragement.
I would like to extend my appreciation to the following institutions, which made vital financial
contributions to this research project: Roberto Rocca Education Programme, Alßan Programme
(scholarship E05M060379AR), The University of Birmingham, and Universidad Tecnológica Nacional
(UTN-FRBA).
I must acknowledge the help I received from members of the Centre for Electron Microscopy, specially
Ms. M.Q. Chu and Dr. Y.Y. Tse, and also Dr. J. Bowen and Dr. X. Y. Li, for their help with different
microscopy techniques. I am also grateful to Dr. V. R. Machavaram, Dr. L. Wang and Prof. G. F.
Fernando, whose assistance was very important for the development of the optical fibre probe; and I am
enormously thankful to Prof. N. Braithwaite, from the Open University, for his valuable discussions and
advice on electrostatic plasma diagnostic techniques.
It would be unfair not to mention here the constant help and support I received from all the academic
community in Metallurgy and Materials, especially from research fellows, technicians and colleagues.
This project would simply not have been possible without them; and I want to thank Mr. M. T.
Cunningham in particular for keeping an eye on, virtually, every daily issue.
Finally, I would like to express my deepest gratitude to my family and friends, for their joy in the
moments of success and their support in the difficult times.
TABLE OF CONTENTS
CHAPTER 1: INTRODUCTION 1
CHAPTER 2: LITERATURE REVIEW 3

1. Stainless steel 3
1.1. Introduction, history and development 3
1.2. Classification 5
1.2.1. Martensitic stainless steels 6
1.2.2. Controlled transformation and precipitation hardening stainless steels 8
1.2.3. Ferritic stainless steels 9
1.2.4. Duplex stainless steels 10
1.2.5. Austenitic stainless steels 11
1.3. Metallurgical aspects and properties of ASS – AISI 316 12
1.3.1. Martensite 13
1.3.2. Carbides 15
1.3.3. Intermetallics 17
1.4. Corrosion properties of AISI 316 18
1.5. Tribological properties of AISI 316 22
2. Surface engineering 27
2.1. Introduction and basic concepts 27
2.2. Thermochemical and diffusion surface engineering treatments 29
2.3. Low temperature thermochemical surface engineering of austenitic stainless steels 31
2.3.1. Rationale of low temperature treatments 31
2.3.2. Metallurgical aspects of expanded austenite 32
2.3.3. Properties and applications of expanded austenite 35
2.4. Common processes to produce expanded austenite 37
2.5. Plasma surface engineering 38
2.6. Active screen plasma technology 41
3. Fundamentals of plasma physics 44
3.1. Plasma 44
3.2. Electric breakdown 46
3.3. Structure of the glow discharge 47
3.4. Plasma diagnostics 49
3.4.1. Optical emission spectroscopy 50
3.4.2. Electric probes 53
CHAPTER 3: EXPERIMENTAL PROCEDURES 57

1. Sample preparation 57
1.1. AISI 316 coupon samples 57
1.2. Friction force samples 58
1.3. Corrosion samples 58
1.4. Transmission electron microscopy (TEM) samples 58
1.5. Residual stresses (RS) bending thin disc samples 59
1.6. Other samples 60
2. Surface engineering plasma treatments: experimental procedures 60
3. Characterisation techniques 62
3.1. Hardness 62
3.2. Roughness 63
3.3. Atomic force microscopy (AFM) 63
3.4. X-ray diffraction (XRD) 63
3.5. Glow discharge optical emission spectroscopy (GDOES) 63
3.6. Optical microscopy (OM) 63
3.7. Scanning electron microscopy (SEM) 64
3.8. Energy dispersive X-ray spectroscopy (EDX) 64
3.9. Electron back scattered diffraction (EBSD) 64
3.10. Transmission electron microscopy (TEM) 64
4. Tribological properties: experimental procedures 65
4.1. Wear tests 65
4.2. Friction tests 66
5. Corrosion behaviour: experimental procedures 66
5.1. Corrosion tests in boiling acid solution 66
5.2. Corrosion tests in acid at room temperature 68
6. Plasma diagnostics – experimental procedures 68
6.1. Optical emission spectroscopy (OES) 68
6.2. Ion flux probe (IFP) 70
CHAPTER 4: RESULTS 73
1. Processing 73
2. Characterisation of plasma carburised AISI 316 75
3. Study of the mechanisms of active screen plasma surface engineering 78
4. Tribological properties 81
5. Corrosion behaviour 86
6. Plasma diagnostics – Optical emission spectroscopy 90
7. Plasma diagnostics – Ion flux probe 92
CHAPTER 5: INTERPRETATION AND DISCUSSION 94

1. Active screen processing conditions 94
2. Carbon expanded austenite 97
2.1. Layer growth kinetics 97
2.2. Microstructure evolution 99
2.3. Residual stresses 102
3. Tribological properties 106
3.1. Wear of AISI 316 untreated substrate 106
3.2. Tribological properties of the expanded austenite layer 108
4. Corrosion behaviour 111
4.1. Corrosion behaviour of AISI 316 untreated substrate in different acid solutions 111
4.2. Corrosion behaviour of carbon expanded austenite: outmost layer 112
4.3. Defects in the expanded austenite layer 114
4.4. Effect of deformation and precipitation of carbides 116
5. Plasma diagnostics: optical emission spectroscopy (OES) 118
5.1. Plasma chemistry 118
5.2. Emission intensity maps 119
6. Plasma diagnostics: Ion flux probe (IFP) 121
7. Mechanisms of active screen plasma surface engineering 124
7.1. Active screen plasma nitriding (ASPN) 124
7.2. Active screen plasma carburising (ASPC) 128
CHAPTER 6: SUMMARY AND CONCLUSIONS 132
CHAPTER 7: PROPOSALS FOR FUTURE WORK 136
LIST OF REFERENCES 137
TABLES 163
FIGURES AND ILLUSTRATIONS 175
APPENDICES 258
Appendix A 258
Appendix B 263
Appendix C 267
List of tables
Table 2.3-1: Typical commercial austenitic stainless steels compositions

Table 2.3-2: Tentative list of precipitates significant to austenitic stainless steels
Table 3.1-1: Commercial specification and chemical composition of the samples
Table 3.2-1: DC carburising and nitriding treatment conditions
Table 3.2-2: Active screen plasma carburising assessed treatment conditions
Table 3.2-3: Active screen plasma nitriding assessed treatment conditions
Table 3.2-4: Active screen mechanisms: assessed treatment conditions
Table 3.3-1: Instrumented hardness settings
Table 3.3-2: Stylus profilometer settings for different measurements
Table 3.3-3: AFM settings
Table 3.3-4: XRD settings
Table 3.3-5: SEM and EBSD camera settings for crystal orientation maps
Table 3.4-1: Composition and properties of WC-Co binder bearing balls used for wear and friction tests
Table 3.6-1: Optronic Labs OL 730-9Q reflex telescope - Technical specifications
Table 3.6-2: Jobin Yvon Triax 180 monochromator - Technical specifications
Table 3.6-3: Jobin Yvon Spectrum ONE detector and CCD3000 controller unit specifications
Table 3.6-4: OES calibration conditions
Table 4.1-1: Constants of equations (4.1-1) to (4.1-3) depending on the gas mixture
Table 4.1-2: ASPC layer thickness (GDOES) after treatment under different conditions
Table 4.1-3: ASPN layer thickness (SEM) after treatment under different conditions
Table 4.1-4: Mean residual stresses measured from the bending of thin discs after ASPC
Table 4.2-1: Instrumented indentation results from AISI 316 UT and AISI 316 PC samples
Table 4.3-1: Roughness measured on Cu samples after treatment under different conditions
Table 4.4-1: Assessed conditions and summary of pin-on-disc wear results
Table 4.4-2: Composition of wear debris (EDX) for AISI 316 UT and AISI 316 PC
Table 4.4-3: Summary of results obtained on the wear debris
Table 4.4-4: Summary of friction results
Table 4.5-1: Corrosion factor for corrosion tests in boiling 16% H2SO4 with CuSO4 for 20 hours
Table 5.1-1: Electric parameters in DC and AS furnaces under similar discharge conditions
Table 5.2-1: Carbon diffusivity calculated from different treatment conditions
Table 5.2-2: Lattice expansion measured on EA from the XRD peak shift
Table 5.2-3: Parameters used for estimation of residual stresses from the instrumented indentation test
Table 5.5-1: Bond enthalpies
List of figures and illustrations
Figure 2.1.1-1: Historical evolution of materials and their relative importance

Figure 2.1.1-2: Young’s modulus - Strength materials selection chart
Figure 2.1.1-3: Fracture toughness – Young’s modulus materials selection chart
Figure 2.1.1-4: Strength - Density materials selection chart
Figure 2.1.1-5: Strength - Relative cost materials selection chart
Figure 2.1.1-6: Corrosion resistance materials selection chart
Figure 2.1.2-1: Schaeffler diagram for stainless steel classification
Figure 2.1.3-1: Fe-Cr-Ni ternary phase diagram
Figure 2.1.3-2: Schematics of Ms and Md for martensitic transformation in ASS
Figure 2.1.3-3: Stress induced martensitic transformation of ASS at different temperatures
Figure 2.1.3-4: Solubility of carbon in austenitic stainless steel 18/8
Figure 2.1.3-5: Reference carbide precipitation sequence
Figure 2.1.3-6: Ageing times for phase precipitation in AISI 316 at 550ºC and 600ºC
Figure 2.1.4-1: Schematics of polarisation curve of ASS in sulphuric acid
Figure 2.1.4-2: Effect of alloying elements on the polarisation curve of ASS
Figure 2.1.4-3: Metallurgical features detrimental to the corrosion resistance of ASS
Figure 2.1.5-1: Wear resistance materials selection chart
Figure 2.1.5-2: Wear rate transitions
Figure 2.1.5-3: Transfer of material between interacting asperities and deformation of the subsurface
Figure 2.2.2-1: Schematic of the stress and mechanical strength diagram for a cross section of a surface
engineered component between the neutral axis and the surface
Figure 2.2.2-2: Typical thickness obtained with surface engineering processes
Figure 2.2.2-3: Energy content - Strength chart for different materials
Figure 2.2.2-1: Schematic representation of the reaction steps in gas carburising
Figure 2.2.3-1: Metal-metal oxide equilibrium curves in hydrogen atmospheres
Figure 2.2.3-2: Threshold Temperature-time curves to produce precipitation free microstructures upon plasma
nitriding (PN) and plasma carburising (PC) on AISI 316
Figure 2.2.3-3: GDOES composition depth profile of AISI 316 plasma carburised and plasma nitrided
Figure 2.2.5-1: Current - Voltage characteristic curve for DC plasma
Figure 2.2.6-1: DC and AS furnaces for plasma carburising (DCPC and ASPC)
Figure 2.3.1-1: Maxwell electron energy distribution function – up: most probable velocity, ū: average velocity,
ueff: r.m.s. velocity
Figure 2.3.1-2: Typical Pashen curve
Figure 2.3.3-1: Structure of the glow discharge
Figure 2.3.4-1: Diagram of electronic, vibrational and rotational energy levels of a molecule
Figure 2.3.4-2: Typical OES equipment
Figure 2.3.4-3: Typical electric probes – (a) plane, (b) cylindrical, (c) spherical
Figure 2.3.4-4: Typical current voltage curve obtained with an electric probe
Figure 2.3.4-5: Ion flux probe
Figure 3.1.3-1: Schematics of corrosion samples
Figure 3.2.1-1: (a) Klöckner Ionon DC furnace and (b) Plasma Metal active screen industrial unit
Figure 3.2.1-2: (a) DC, (b) AS and (c) FP arrangements inside a conventional DC plasma furnace used to study
the mechanisms of active screen plasma treatments.
Figure 3.2.1-3: DC, AS and FP arrangements inside a conventional DC plasma furnace used to study the
mechanisms of active screen plasma treatments.
Figure 3.2.1-4: Fish bone diagram of the treatment conditions involved
Figure 3.4-1: Schematics of the pin-on-disc apparatus used for wear and friction tests
Figure 3.5-1: Schematics of the apparatus used for immersion corrosion in boiling acid solutions
Figure 3.6-1: Experimental arrangement used for OES (telescope) and IOES (optical fibre probe)
Figure 3.6-2: DC and AS experimental arrangements used for IFP measurements
Figure 4.1-1: ASPC processing conditions on the work table
Figure 4.1-2: ASPN processing conditions on the work table
Figure 4.1-3: Samples in a DC conventional treatment, showing arcing on a dirty or rusty specimen, and
hollow cathode effect on a sample with a blind hole.
Figure 4.1-4: Surface damage by process instabilities in DC conventional treatments
Figure 4.1-5: Layer thickness (size of the bubble) superimposed on the map of treatment conditions for ASPC
and ASPN
Figure 4.1-6: Typical profile of the thin discs used for the assessment of residual stresses
Figure 4.2-1: Optical micrographs of the same area before and after plasma carburising
Figure 4.2-2: EBSD crystal orientation maps of the same area before and after plasma carburising
Figure 4.2-3: GDOES composition-depth profiles for different treatment times: (A) 1 hour, (B) 3 hours and (C)
6 hours
Figure 4.2-4: Typical cross section micrograph of an AISI 316 plasma carburised specimen
Figure 4.2-5: SEM micrographs of DCPC and ASPC treated samples
Figure 4.2-6: AFM images of DCPC and ASPC treated samples
Figure 4.2-7: TEM micrograph and diffraction pattern (amorphous) of the oxide layer on DCPC and ASPC
samples
Figure 4.2-8: TEM micrograph and ring electron diffraction pattern on a plasma carburised specimen
Figure 4.2-9: Electron diffraction pattern of the carbon expanded austenite on a plasma carburised specimen
Figure 4.2-10: XRD pattern obtained on DCPC and ASPC, and austenite reference pattern
Figure 4.2-11: Lattice parameter ahkl vs cosθ.cotθ of expanded austenite and AISI 316 UT
Figure 4.2-12: GDOES composition-depth profile of DCPC and ASPC treated samples
Figure 4.2-13: Load bearing capacity (LBC) of DCPC and ASPC treated samples
Figure 4.2-14: Cracks inside a low-force (500g) Vickers indentation on a DCPC sample
Figure 4.2-15: Instrumented hardness on AISI 316 untreated and ASPC treated samples
Figure 4.3-1: Appearance of the samples treated under DC and AS arrangements in nitriding, carburising and
nitrogen enhanced carburising atmospheres
Figure 4.3-3: GDOES composition-depth profiles of samples treated under DC and AS arrangements in
nitriding, carburising and N2 enhanced carburising atmospheres
Figure 4.3-4: Load bearing capacity (LBC) of samples treated under DC and AS arrangements in nitriding,
carburising and N2 enhanced carburising atmospheres
Figure 4.3-5: Optical micrograph of a hardness indent on one AISI316 sample after ASPN
Figure 4.3-6: Vickers microhardness tests on different parts of the AISI 304 stripe specimens treated in an AS
arrangement with big holes in the mesh
Figure 4.3-7: Optical micrographs of the deposition layer on ASPN, ASPC and ASPCN copper samples
Figure 4.3-8: Morphology of AS nitrided, carburised and N2 enhanced carburised samples observed under
SEM and AFM
Figure 4.3-9: XRD patterns of copper samples treated under DC and AS arrangements in nitriding, carburising
and N2 enhanced carburising atmospheres
Figure 4.3-10: ASPC and ASPN treated glass slides
Figure 4.3-11: XRD peaks of the deposition layer on ASPN treated glass slides
Figure 4.3-12: Micrograph and EDX spectrum of the mesh material used in the AS experiments
Figure 4.3-13: Micrograph and EDX spectrum of the mesh material used in the AS industrial unit
Figure 4.4-1: Typical appearance of the wear tracks on AISI 316 UT and AISI 316 PC
Figure 4.4-2: Appearance of the WC-Co ball worn against AISI 316 UT and AISI 316 PC
Figure 4.4-3: Measured worn volume after pin-on-disc test
Figure 4.4-4: SEM images of the wear tracks on AISI 316 UT and AISI 316 PC
Figure 4.4-5: EDX maps on the wear track left on AISI 316 PC worn against WC-Co ball
Figure 4.4-7: SEM images of the wear scars on WC-Co balls worn against AISI 316 UT and AISI 316 PC
Figure 4.4-8: SEM images of the material accumulated at the trailing edge of the wear scar left on WC-Co
balls worn against AISI 316 UT and AISI 316 PC
Figure 4.4-9: EDX map of the wear scar left on the WC-Co ball worn AISI 316 UT
Figure 4.4-10: EDX map of the wear scar left on the WC-Co ball worn against AISI 316 PC
Figure 4.4-11: Wear debris from untreated and carburised AISI 316 respectively
Figure 4.4-12: SEM BSE micrograph of wear debris from AISI 316 UT and AISI 316 PC
Figure 4.4-13: Electron diffraction patterns on wear debris from AISI 316 UT and AISI 316 PC
Figure 4.4-14: TEM micrograph of wear debris from AISI 316 PC and the EDX spectrum
Figure 4.4-15: XRD pattern of the deformed material on the wear track of AISI 316 UT
Figure 4.4-16: Hardness profile measured on the cross section of one AISI 316 UT sample worn against WC-Co
Figure 4.4-17: SEM cross section image of the wear track of AISI 316 UT worn against WC-Co
Figure 4.4-18: EBSD crystal orientation maps of the distorted layer, and martensite phase map on the cross
section of the wear track of one AISI 316 UT specimen.
Figure 4.4-19: EBSD orientation maps on cross sections of one AISI 316 PC specimen: wear track and treated
layer
Figure 4.4-20: Coefficients of friction obtained from different material pairs
Figure 4.5-1: Immersion corrosion test in H2SO4 16% solution at room temperature for 120 h - AISI 316: Attack
on a MnS inclusion; ASPC: deposition layer of carbides pealing off
Figure 4.5-2: Surface appearance of AISI 316, DCPC 400, ASPC 125 and ASPC 030 specimens corroded in
boiling H2SO4 16% solution
Figure 4.5-3: Cross section of AISI 316 UT and PC specimens exposed to boiling H2SO4 16% solution for 1 h
Figure 4.5-4: Cross section of a PC specimen exposed to boiling H2SO4 16% solution for 1 h - Localised attack
on MnS inclusions
Figure 4.5-5: Cross section of a PC specimen corroded in boiling H2SO4 16% solution for 1 h - Localised
attack on slip bands
Figure 4.5-6: Plan view of a PC specimen immersed in boiling H2SO4 16% solution for 15 h - Localised attack
on grain boundaries
Figure 4.5-7: Cross section of a PC specimen corroded in boiling H2SO4 16% solution for 1 h - Corrosion
progressing through grain boundaries of the AISI 316 substrate once the EA layer had been
penetrated
Figure 4.5-8: Rod samples used for corrosion tests in boiling H2SO4 16% solution
Figure 4.5-9: Mass loss specimens after immersion corrosion test in boiling H2SO4 16% solution for 20 h
Figure 4.5-10: Coupon samples exposed to boiling H2SO4 16% solution with CuSO4 for 20 h
Figure 4.5-11: Optical micrographs of specimens corroded in boiling H2SO4 16% solution with CuSO4 for 20 h
Figure 4.5-12: SEM micrograph of pits coalescing at the intersection of slip bands with a grain boundary, and
AFM image of the attack on slip bands and formation of ditch grain boundary
Figure 4.5-13: SEM micrograph of a ditch type grain boundary and EDX Carbon line scan on a similar boundary
Figure 4.5-14: SEM micrographs of samples corroded in boiling HNO3 20% solution for 240 h
Figure 4.5-15: AFM image of localised corrosion at grain boundaries and cross section data - Sample DCPC
400 after immersion corrosion test in boiling HNO3 20% solution for 240 hours
Figure 4.5-16: Localised attack on samples exposed to boiling HNO3 20% solution for 240 hours
Figure 4.5-17: Corrosion rates for specimens immersed in boiling HNO3 20% solution for different periods of
time
Figure 4.6-1: Low and high resolution spectra for plasma carburising
Figure 4.6-2: Low and high resolution spectra for nitrogen enhanced plasma carburising
Figure 4.6-3: Low and high resolution spectra for plasma nitriding
Figure 4.6-4: Simplified emission intensity map obtained for ASPN
Figure 4.6-5: Summary of the OES intensity maps obtained under ASPC and ASPN treatment conditions
Figure 4.6-6: Correlation between OES emission intensity and the electric parameters of the furnace under
ASPC and ASPN treatment conditions
Figure 4.7-1: Oscillations in the floating potential measured with the IFP under DC and AS arrangements
inside a DC furnace.
Figure 4.7-2: Floating potential and ion flux measured under DC and AS experimental arrangements inside a
DC furnace, in carburising and nitriding gas mixtures
Figure 4.7.3: Oscillations observed in the FP of the IFP inside the AS industrial unit
Figure 4.7-4: Average FP measured with the IFP under different ASPC and ASPN conditions
Figure 4.7-5: IFP drain curves obtained at floating potential in ASPC and ASPN conditions
Figure 4.7-6: Ion flux calculated from the drain curves of the IFP in ASPC and ASPN conditions
Figure 5.1-1: I-V electric curves obtained for ASPC and ASPN at different gas pressures
Figure 5.1-2: Bias set point and real bias power applied for ASPC and ASPN conditions
Figure 5.1-3: Bias current vs bias set point for ASPC and ASPN
Figure 5.1-4: Worktable power for different ASPC and ASPN treatment conditions (bias levels and pressures)
Figure 5.1-5: Characteristic I-V curves for ASPC and ASPN with E/p as bubble size
Figure 5.2.1: Layer thickness vs treatment time
Figure 5.2-2: EBSD pattern quality - Carbon concentration at plateau (GDOES carbon profile)
Figure 5.2-3: Optical micrograph on a plasma carburised specimen
Figure 5.2-4: XRD pole figures obtained on AISI 316 UT and AISI 316 PC
Figure 5.2-5: AFM image of a grain with activated crossed slip systems and cross section profiles
Figure 5.2-6: AFM plane view of PC samples and crystal mimic obtained from EBSD COMs
Figure 5.2-7: Misorientation measured by EBSD on the same area of the sample before and after plasma
carburising
Figure 5.2-8: EBSD crystal orientation (normal direction) before and after PC respectively
Figure 5.2-9: CSL Σ3 grain boundaries before and after PC respectively
Figure 5.2-10: Distribution of residual stress: average, triangular, GDOES and strain hardened profiles
Figure 5.2-11: Hardness profiles calculated from LBC and Knoop hardness profile
Figure 5.2-12: Estimation of residual stresses from instrumented indentation tests
Figure 5.3.1-1: SE image of the cross section of a wear track on AISI 316 UT with EBSD COM superimposed
and inverse pole figure obtained from that same area of the sample
Figure 5.3.1-2: Signs of accumulated plastic strain (3 steps of deformation) at the edge of the wear track of AISI
316 UT, and schematics of the deformation in the subsurface region.
Figure 5.3.2-1: Failure of the layer of carbides at the edge of a wear track on AISI 316 PC
Figure 5.3.2-2: Smooth surface of the underlying EA layer, and protective oxide layer formed during sliding wear
Figure 5.3.2-3: Genesis of the protective oxide layer on a PC specimen
Figure 5.3.2-4: Detachment of WC particles from the counterpart ball
Figure 5.3.2-5: Morphology of the protective oxide layer on a PC specimen under AFM
Figure 5.3.2-6: Crack propagation along the original deformation morphology in the protective oxide layer
Figure 5.3.2-7: Process of detachment of wear debris from the protective oxide layer. SEM image and
schematics
Figure 5.3.2-8: Cracks on a thick portion of the protective oxide layer
Figure 5.4.1-1: Corrosion potential of ASS in different acid solutions vs saturated calomel electrode
Figure 5.4.2-1: SEM micrograph and chemical composition according to EDX of material pealed off from a PC
sample at early stages of a corrosion test in boiling sulphuric acid
Figure 5.4.2-2: XPS spectrum obtained from the surface of an ASPC sample
Figure 5.4.3-1: Schematics of the corrosion mechanisms observed on carbon expanded austenite
Figure 5.4.3-2: Morphology of specimens corroded in boiling H2SO4 16% solution with CuSO4
Figure 5.4.4-1: Inverse pole figures obtained by EBSD on the same area of the sample before and after PC
Figure 5.4.4-2: Fraction number of special grain boundaries before and after PC
Figure 5.4.4-3: Edge effect revealed by microhardness measurements across the surface of a DCPC
sample
Figure 5.5.2-1: Optical emission spectra collected at different gas pressures in a 75% N2- 25% H2 gas mixture
Figure 5.7.1-1: Morphology of the deposition layer under different ASPN treatment conditions
Figure 5.7.1-2: Deposition layer on grains with different crystallographic orientations
Figure 5.7.1-3: Sputtering and redeposition model for DC and AS plasma nitriding
Figure 5.7.1-4: Deposition layer on a glass slide treated in an AS arrangement with an AISI 304 mesh
Figure 5.7.1-5: Deposition layer (EDX) vs expanded austenite layer thickness (GDOES)
Figure 5.7.1-6: Detachment of the deposition layer of iron nitrides AS plasma nitrided at floating potential
Figure 5.7.2-1: TEM micrograph of the deposited particles and EDP
Figure 5.7.2-2: SEM micrograph and XRD pattern from carbide film deposited on the walls of the AS furnace
List of abbreviations and acronyms
AFM Atomic Force Microscopy

AS Active Screen
ASP Active Screen Plasma
ASPC Active Screen Plasma Carburising
ASPCN Active Screen Plasma Nitrogen enhanced Carburising
ASPN Active Screen Plasma Nitriding
ASS Austenitic Stainless Steel
BS British Standards
BSE Back Scattered Electron (imaging)
CCD Charge - Coupled Device
CF Corrosion Factor
COF Coefficient of Friction
COM Crystal Orientation Map
CSL Coincident Site Lattice
CVD Chemical Vapour Deposition
DC Direct Current
DCPC Direct Current Plasma Carburising
DCPCN Direct Current Plasma Nitrogen enhanced Carburising
DCPN Direct Current Plasma Nitriding
EA Expanded Austenite
EBSD Electron Back Scattered Diffraction
EDP Electron Diffraction Pattern
EDX Energy Dispersive X-Ray spectroscopy
EEDF Electron Energy Distribution Function
fcc face centred cubic
FEG Field Emission Gun
FP Floating Potential
GDOES Glow Discharge Optical Emission Spectroscopy
IFP Ion Flux Probe
LBC Load Bearing Capacity
LTE Local Thermal Equilibrium
MS Martensitic transformation Start temperature
MF Martensitic transformation Finish temperature
OES Optical Emission Spectroscopy
OM Optical Microscopy
PC Plasma Carburising
PE Para - Equilibrium
PIPS Precision Ion Polishing System
PMT Photo Multiplier Tube
PN Plasma Nitriding
PSE Plasma Surface Engineering
PVD Physical Vapour Deposition
RS Residual Stresses
SE Surface Engineering
SEI Secondary Electron Image
SEM Secondary Electron Microscopy
TEM Transmission Electron Microscopy
UT Un-Treated substrate material (in reference to AISI 316)
XRD X-Ray Diffraction
CHAPTER 1: INTRODUCTION
Austenitic stainless steels are commonly selected because of their high corrosion resistance, which is
the main advantage of these alloys. On the other hand, low hardness and wear resistance are usually
mentioned among their downsides. Surface engineering processes have been traditionally used to
improve these aspects. Furthermore, thermochemical treatments conducted at low temperature are a
valuable method to improve the tribological performance of austenitic stainless steel, without affecting
the corrosion behaviour of this alloy. This is achieved by the formation of a supersaturated solution of
carbon or nitrogen in austenite, usually called expanded austenite, which confers significant hardening,
increased tribological performance, and corrosion resistance comparable or even superior to the
untreated substrate.
Several processes can be used to produce the so called expanded austenite layers. The evidence
indicates that plasma treatments outperform the conventional gas processes in terms of operative costs
and environmental friendliness. DC plasma thermochemical treatment is a well-established technology,
although some intrinsic defects of this technique, such as edge effects, hollow cathode effects and
arcing, have blighted their industrial potential. To this end, a novel active screen plasma technique has
shown its potential to solve the problems of DC plasma treatments. The benefits are principally related
with a considerable improvement in the surface quality and the uniformity of the diffusion layer.
Whilst most of the work on active screen has been focused on nitriding, very little work has been
conducted on active screen plasma carburising. The latter treatments are of interest because they
produce thicker layers of expanded austenite, with a smoother gradient of chemical composition and
mechanical properties. Thus, carbon expanded austenite shows hardening effect, wear resistance and
Chapter 1: Introduction Page 1

corrosion resistance comparable to nitrogen expanded austenite, but with increased layer thickness and
additional load bearing capacity. Moreover, the better surface quality obtained with active screen
plasma carburising, compared with the DC plasma technique, yields greater improvement in the
performance of the substrate.
Even though the effectiveness of the active screen plasma technology is a fact, the mechanisms
involved in this treatment remain unclear. This makes it difficult to optimise the processing conditions,
and it also generates some scepticism among the potential users. Therefore, the present work has been
directed at developing active screen plasma carburising (ASPC) technology to enhance the corrosion
and wear properties of austenitic stainless steel. The scientific and technological objectives of the
present project are the following:
To explore the feasibility of active screen plasma carburising of AISI 316 austenitic stainless
steel, to form carbon expanded austenite.
To study the effect of different treatment parameters (i.e. pressure, gas composition and
bias) on the ASPC process and optimise it.
To conduct systematic characterisation on ASPC treated materials.
To assess the wear and corrosion properties of the ASPC treated AISI 316 austenitic
stainless steel.
To develop and use plasma diagnostic techniques to evaluate the active species in ASP and
advance the scientific understanding of carbon mass transfer and carburising mechanism
involved in ASPC.
Chapter 1: Introduction Page 2

CHAPTER 2: LITERATURE REVIEW
1. Stainless steel
1.1. Introduction, history and development
There is no doubt that the field of materials engineering is now developing faster than at any other time
in the history of mankind, and that the rate of innovation continues to accelerate. The diagram in figure
2.1.1-1 summarises the historical evolution of the different classes of materials [1]. The increasing
number of choices of materials provides a better coverage of the applications’ demands, but this also
represents a great challenge for design engineers to select the optimum one.
The difficulties associated with the selection of engineering materials have been addressed by Ashby in
his book Materials selection in mechanical design. The use of indices based on the materials properties,
relevant for a given application, helps in the identification of the most convenient class of materials.
Furthermore, by plotting these indexes in so called materials selection charts, the range of applicability
for each material class becomes evident. Some of these charts will be used here as a reference frame
for the material of interest to this thesis, i.e. austenitic stainless steel.
With regard to physical and mechanical properties, it is possible to say, from the charts displayed in
figures 2.1.1-2 to 2.1.1-4, that steel covers a wide range of strength values, with a high level of stiffness
and toughness, only penalised by its high density. In addition to this, figure 2.1.1-5 shows that the
relative cost of steel is low compared to other engineering alloys, although this chart is not updated and
the information is not as reliable as the other three charts.
Chapter 2: Literature review Page 3

In any case, it is this combination of good mechanical properties and low cost which makes steel an
extremely valuable material for engineering applications, and stainless steel inherits these general
properties, to some extent. However, it is its high corrosion resistance that makes stainless steel unique.
As it can be seen from the materials selection chart in figure 2.1.1-6, stainless steel shows excellent
corrosion resistance in a wide range of harsh environments, putting it ahead of other engineering alloys.
For over a hundred years, several scientists (including Berthier, Baur, Hadfield, Osmond, Faraday and
Stodart) had collected evidence regarding the corrosion properties of iron-chromium alloys, but it was
not until early in the 20th century that the commercial potential of such material became evident [2, 3].
Harry Brearley is usually referred to as the inventor of a ferritic Fe - 13% Cr alloy firstly called “rustless
steel”, which subsequently became “stainless steel”. Although the discovery of the alloy is disputed by
Strauss, Maurer and Monnartz, Brearley was undoubtedly the first one to identify an application and to
commercialise stainless steel products, in the form of cutlery. In Germany, Maurer and Strauss
developed, in parallel, an austenitic alloy of Fe-Cr-Ni, which was soon applied in the food and chemical
industries, in Europe and in the United States.
From then onwards, the development of stainless steel was very fast, impelled by the great number of
industrial and domestic applications. Significant work was conducted to research and develop ferritic,
martensitic and the well known austenitic alloys with a number of different alloying elements. In all
cases, high chromium contents in excess of 10% are required to form a stable passive oxide film on the
surface and exert the characteristic resistance to corroding agents [4].
There is no doubt that the distinct property of stainless steels is their corrosion resistance. As it is usual
in engineering applications, this property is attained at the expense of other factors, such as hardness,

strength, toughness, weldability, formability, creep resistance, etc. Consequently much of the work done
on stainless steel has been focused on improvements of these other mechanical, engineering and
manufacturing characteristics [5].
An impressive level of refinement has been achieved in the metallurgical practices to produce stainless
steel with a wide range of properties. In the next section, stainless steels of different compositions and
phases will be introduced, and a summary of their advantages, disadvantages and applications will be
presented.
1.2. Classification
Stainless steels are usually classified according to their phase constitution, i.e. martensitic, ferritic,
austenitic or duplex. The stability of these phases is dictated by the alloying elements, which can be
separated in two main groups: α forming elements and γ forming elements [6]. Two main constituents of
stainless steels, chromium and nickel, head each group, and it is customary to express the contribution
made by all the elements in the alloy as chromium equivalent and nickel equivalent according to the
following equations:
%Cr ⋅ equivalent = (Cr ) + 2 ⋅ (Si ) + 1.5 ⋅ (Mo) + 5 ⋅ (V ) + 5.5 ⋅ ( Al ) + 1.75(Nb) + 1.5(Ti ) + 0.75(W ) (2.1-1)
% Ni ⋅ equivalent = (Ni ) + (Co ) + 0.5 ⋅ (Mn ) + 0.3 ⋅ (Cu ) + 25 ⋅ (N ) + 30 ⋅ (C ) (2.1-2)
where the element symbols between brackets represent the alloy composition expressed as mass
fraction (wt%).

By plotting these two parameters, the Schaeffler diagram shown in figure 2.1.2-1 is obtained, which
gives a rough but generally good map of the phases that can be expected for a given alloy composition
and, consequently, its mechanical properties. In this way, it is possible to see that high chromium
equivalents render martensitic and ferritic structures, while high nickel equivalents stabilise the
austenitic phase. Notwithstanding, the design of the alloy composition is a rather more complicated
matter which involves both technical and economical factors. It is usually intended to produce the best
possible material for a given application at the lowest possible cost and, as it is the case for most
engineering alloys, heat treatments play an important role in this regard.
It is important to mention that other phases, intermetallic compounds, carbides and nitrides are
commonly found in the Fe-Cr-Ni system with addition of other alloying elements, e.g. Ti, V, Mo, Co, Mn,
Al, Nb, C, N. Although present in only small fractions, these secondary phases can significantly affect
the metallurgical characteristics, corrosion properties and mechanical properties of stainless steels.
Some of them will be briefly introduced in the following sections.
In what follows, each one of the generic categories of stainless steel will be examined in some further
detail.
1.2.1. Martensitic stainless steels [5-8]
These alloys typically contain 12% to 17% Cr and 0.1% to 1.0% C with additions of other alloying
elements such as Mo, V, Nb, Al and Cu. The austenitic structure, which is stable over 1050ºC,
undergoes full martensitic transformation on cooling, producing components with high strength and
hardness, but also low toughness. Therefore, it is necessary to temper these alloys at the highest

possible temperature in order to obtain a good combination of mechanical properties, namely strength,
toughness and ductility.
Alloying elements such as Mo, W, V and Nb are of interest to increase the tempering resistance by
secondary hardening reactions, which increase the strength but also reduce the toughness and the
resistance to stress corrosion. In addition, their tendency to retain δ ferrite has to be balanced by
austenite forming elements. The allowable amount of C and N is limited because these elements
significantly reduce the toughness, so that Ni, Co, Mn and Cu have to be used, thus increasing the cost
of the alloy. In addition, this introduces another detrimental effect since the MS - MF temperature range is
depressed, thus a small fraction of austenite can be retained at grain boundaries and subsequently
transformed to martensite during tempering, causing distortion and embrittlement. The austenite forming
elements also lower the AC1 temperature, and consequently limit the range of tempering conditions.
This rather delicate balance between alloying elements acquires one more degree of complexity when
considering the precipitation hardening effects associated with additions of Ti, Al, Cu and Mo. The
precipitation of intermetallic compounds provides an alternative hardening and strengthening
mechanism, independent of the carbon content. The strength and ductility can usually be tailored by
changing the tempering temperature, although some large intermetallic particles (Fe2Mo) and secondary
phases (Cr rich α’-phase, Fe-Cr-Mo χ-phase) can form on over-ageing, leading to severe embrittlement.
In summary, the advantage of martensitic stainless steels is their high strength and high hardness, but
this is achieved at expense of the corrosion resistance. The applications include tools, gears, shafts,
valves, bearings, engine and wear resistant parts in chemical and petrochemical industries,
hydroelectric power generation and aeronautic applications.

1.2.2. Controlled transformation and precipitation hardening stainless steels [5, 6, 8]
Martensitic stainless steel components were found to be difficult to produce in the fully hardened
condition, and complex shapes could not be heat treated without severe distortions. Therefore, there
was a requirement for a stainless steel with a preliminary austenitic structure to permit good formability,
which could subsequently undergo martensitic transformation and produce precipitation hardening,
keeping a high tempering and corrosion resistance. It is not difficult to recognise the metallurgical
challenges associated with such requirements.
In order to fulfil the specifications, the alloy requires low C content and 16% to 19% Cr, balanced with
austenite forming elements (typically 4% to 7% Ni and/or Mn) to reduce the tendency to form δ ferrite,
but keeping MS high enough to allow martensitic transformation when necessary. The alloy composition
to produce the right balance between δ ferrite and MS is critical. Furthermore, Mo and V are added for
tempering resistance and Ti, Al, Cu and Co to induce precipitation hardening.
The martensitic transformation can be induced by refrigeration (sub-zero heat treatment) or by a primary
ageing treatment to precipitate M23C6 and control the amount of C in solution, available for the
martensitic transformation (increase in MS). Cold working is an alternative way, though not usually relied
upon because the transformation is not uniform. Although achievable, the accurate adjustment of the MS
- MF temperature range is difficult and requires stringent control of the alloy composition, with an
obvious impact in the economical viability. Therefore, most of these alloys are manufactured in the fully
transformable and precipitation hardened condition.
The applications are very limited and include the skin of high speed rockets and aircraft, high strength
stainless fasteners, wire and cables.

1.2.3. Ferritic stainless steels [5-8]
As their name indicates, these are ferritic alloys up to the melting point, containing 17% to 26% Cr, and
only a small fraction of austenite forms at high temperature depending on the amount of other alloying
elements, mainly C and N. The ferritic structure is stronger than the austenitic one, and the absence of
Ni in their composition represents a significant advantage over the austenitic counterparts in terms of
cost, although they are penalised in corrosion resistance, formability and toughness.
The occurrence of Fe-Cr σ-phase, Fe-Cr-Mo χ-phase and Cr rich α’-phase is of importance in ferritic
stainless steel and can lead to some embrittlement phenomena. Care should also be taken to avoid
embrittlement by martensitic transformation of the retained austenite present at grain boundaries in
alloys with high content of austenite forming elements. Moreover, alloys containing Ni, Co, Mo, Ti, Al
additions precipitate β-phase intermetallic compounds, which together with carbides (M23C6 and M7C3)
and nitrides (M2N) reduce the toughness. This list of embrittlement effects explains why ferritic stainless
steels exhibit ductile to brittle transition temperature, and puts into evidence one of the main weak points
of these alloys: their low toughness.
On the other hand, the same mechanisms that reduce ductility also produce strengthening, so ferritic
stainless steels are superior to the austenitic ones in terms of yield and ultimate stresses. The stacking
fault energy is higher, thus ferritic stainless steels have low work hardening rate, which reduces the flow
stresses upon forming but affects the uniform strain and stretch formability. On hot rolling, a problematic
crystallographic texture called roping develops and, while being very ductile, ferritic stainless steels are
also soft and can get easily marked.

The corrosion resistance of ferritic stainless steels is appropriate in mild corrosive environments,
although in the most severe conditions they do not perform as well as their austenitic counterparts.
Addition of molybdenum increases their corrosion resistance, and stabilisation with Ti and Nb helps to
avoid grain boundary attack due to precipitation of chromium carbides. Perhaps one of the greatest
advantages offered by ferritic stainless steels is their high resistance to stress corrosion cracking,
making them interesting for applications in chemical plants.
Ferritic stainless steels are increasingly displacing austenitic stainless steels in the less demanding
applications, mainly because of economic reasons. Efforts have been made to improve their weldability
and toughness, and thus increase the range of applications, which is for the moment focused on indoor
stainless applications.
1.2.4. Duplex stainless steels [5-9]
Duplex stainless steels were developed in an attempt to fuse in one material the positive aspects of
austenitic and ferritic alloys. Therefore, they are constituted by a ferritic-austenitic or ferritic-martensitic
duplex structure with a typical composition of 18% to 30% Cr, relatively low Ni content and some
additions of Mo, Nb and Ti. The reduction in the amount of Ni provides some cost reduction over the
austenitic stainless steels, while having superior yield and ultimate stresses, and resistance to corrosion
and pitting that compares favourably with the austenitic benchmark alloy.
The presence of ferrite and the induced reduction in the grain size of austenite increases the strength.
Moreover, the austenite undergoes martensitic transformation upon deformation, increasing the strength
to even higher levels than the pure ferritic structures. This is achieved without a significant reduction in
toughness, which is somewhere between the austenitic and ferritic alloys. The physical and mechanical

properties can be widely tailored by changing the volume fraction of each phase, which at the same time
depends on the alloy composition and processing conditions.
The relatively high occurrence of secondary phases is perhaps the weakness of duplex stainless steels,
and several embrittlement effects have been reported in the temperature range 300ºC - 1000ºC, related
to Fe-Cr-Mo σ and χ-phases, Fe-Mo-N π-phase, and some degree of partitioning of alloying elements
between the austenitic and ferritic phases. Nevertheless, appropriate heat treatments and cooling rates
seem to be successful in avoiding or minimising these effects.
The applications of these alloys are expanding and, due to their high corrosion resistance and good
mechanical properties, include: chemical, petrochemical, oil, wood pulp, pharmaceutical, textile and
nuclear industries.
1.2.5. Austenitic stainless steels [4-8, 10, 11]
Austenitic stainless steel (ASS) is undoubtedly the most widely used, and currently accounts for 70% to
80% of the stainless steel world production volume, with its emblematic 18/8 composition, i.e. 18% Cr
and 8% Ni. ASS typically contains 18% to 25% Cr and 8% to 20% Ni, making them fully austenitic and
consequently non-magnetic, although martensitic phase transformation may occur during deformation.
Additions of Mo and other alloying elements further increase its outstanding resistance to general and
pitting corrosion, and it is this property that makes it unique, not so its mechanical properties, which are
meagre.
In general, austenitic stainless steel is the first choice in the most severe corrosive conditions. The C
content of these alloys is usually kept at very low levels to avoid precipitation of Cr23C6 carbides at grain

boundaries, which significantly reduce their corrosion resistance. Ti and Nb can also be added to
produce the so called stabilised grades. The high Ni and Mo contents make ASS an expensive material,
although its relative cost compares favourably with other non-ferrous alloys, e.g. Ni or Ti based alloys.
Some attempts have been made to use Mn, Cu and N to replace Ni in the alloy composition with some
degree of success, although the corrosion resistance is inferior to the traditional Ni alloyed ASS.
To complete the selection grid, ASS is tough and shows no ductile-brittle transition temperature, it is
easily weldable and, having a low yield stress, it exhibits high ductility and is especially suitable for
stretch forming. Nevertheless, its low resistance to stress corrosion cracking, low ultimate stress and
low hardness pose some limitations in its applications.
Being the subject of this research project, the metallurgical aspects, corrosion properties and wear
resistance of ASS, and of AISI 316 in particular, will be discussed in further detail in the following
sections.
1.3. Metallurgical aspects and properties of ASS – AISI 316
The Fe-Ni-Cr ternary phase diagram is the basis for the study of ASS. Additions of Ni and other
austenite stabilising elements expand the γ loop and, with sufficiently large amounts, make the
austenitic structure stable (or metastable) up to room temperature [12]. In general, the effect of alloying
elements depends on the composition of the material to which they are added, and that is the case of
chromium in ASS. Being an α stabilising element, chromium tends to shrink the γ loop, although in the
presence of Ni it retards the γ → α transformation. From the ternary phase diagram in figure 2.1.3-1, it
is possible to conclude that the 18% Cr - 8% Ni composition minimises the amount of Ni for a fully

austenitic structure [4, 13]. This basic 18/8 composition is subsequently modified to obtain the properties
of interest.
The typical chemical compositions of commercial ASS alloys are shown in table 2.3-1. Differences in
composition and processing conditions have a profound effect in the type and volume fraction of the
secondary phases present in the alloy and, consequently, in their physical and mechanical properties
[14]. A detailed and comprehensive description of the secondary phases observed in ASS is out of the
scope of this review and only the ones most significant to the material under study (i.e. AISI 316) will be
discussed, namely: martensite, carbides and intermetallic phases (σ, χ and Laves phases) [15].
1.3.1. Martensite
By calculating the Cr and Ni equivalents with equations (2.1-1) and (2.1-2), and making use of the
Schaeffler diagram in figure 2.1.2-1, it is evident that the basic 18/8 composition of ASS is on the border
line of the pure austenitic structure domain [5]. The Ni content of these ASS is only enough to reduce
MS to just below room temperature, and substantial martensitic transformation takes place if the material
is cooled to sufficiently low temperatures [4]. The MS temperature is determined by the chemical
composition of the alloy and the following equation can be used as a reference [6]:
M S [ o C ] = 502 − 810(C ) − 1230(N ) − 13(Mn) − 30(Ni ) − 12(Cr ) − 54(Cu ) − 6(Mo ) (2.1-3)
where the element symbols between brackets represent the alloy composition expressed as mass
fraction (wt%).

It is interesting to note that all the alloying elements have the same effect: reduce MS and thus stabilise
the austenite against martensitic transformation [16]; the effect of Ni being twofold: it stabilises the
austenitic structure and lowers the MS temperature [5]. In this way, AISI 316 exhibits higher stability to
martensitic transformation, compared to the basic 18/8 AISI 304 [17]. However, the γ (fcc) structure is
said to be metastable at room temperature and martensitic phase transformation can occur on plastic
deformation at temperatures even higher than MS [16].
To explain this phenomenon it is useful to recall the thermodynamic basics of the phase transformation:
in order to happen, the transformation has to reduce the free energy of the system and, at the same
time, sufficient energy must be given for the system to initiate the transformation (activation threshold).
The schematics in figure 2.1.3-2 illustrates these principles, so that if TO is the equilibrium temperature
for the γ and α phases, the transformation will occur spontaneously below MS since the thermal energy
at that point is enough to mount the activation threshold ΔGth. Between TO and MS, the γ phase is not
thermodynamically stable, but the thermal energy is insufficient to initiate the transformation. It is in this
region that the transformation can be activated by plastic deformation, taking the name of strain induced
martensitic transformation [16, 18]. Hence, a reference temperature Md30 can be estimated, from the
alloy composition, using the following equation [6]:
M d 30 [ o C ] = 497 − 462(C + N ) − 9.2(Si ) − 8.1(Mn ) − 13.7(Cr ) − 20(Ni ) − 18.5(Mo ) (2.1-4)
where Md30 is the temperature at which 50% martensite is obtained under a true strain of 0.3, and the
element symbols between brackets represent the alloy composition expressed as mass fraction (wt%).

Figure 2.1.3-3 shows the strain induced martensitic transformation, for a given ASS alloy composition,
as a function of the temperature and the strain [18]. This behaviour was found to be the result of the
competition of two deformation modes. At low temperatures, no slip takes place and all the deformation
is due to martensitic transformation, whilst at higher temperatures, slip becomes dominant and the
martensitic transformation decreases [16].
The inset of martensite has a marked effect in the corrosion and mechanical properties of AISI 316, and
some of these effects will be mentioned in following sections.
1.3.2. Carbides
Carbides and, to lesser extent, nitrides have attracted particular attention in high alloy steels, and ASS
is no exception. The mechanical properties and corrosion performance of ASS are significantly affected
by precipitation of carbides and nitrides, being beneficial at times, but catastrophic in some other cases
[6]. The effect of these phases is very much dependent on their composition, stoichiometry, morphology
and precipitation sites [19]; whilst the kinetics of precipitation is mainly governed by the availability of
carbon, nitrogen and carbide/nitride forming elements in the alloy, together with some energetic
considerations related to diffusion [20, 21].
As it is evident from figure 2.1.3-4, the solubility of carbon in austenite is reduced by the chromium
content, to about 0.05% in the case of the 18/8 ASS [4]. Therefore, carbon contents in the order of
0.05% or higher will remain in solution in the austenitic structure only if the material is solution treated
and quenched. However, during heat treatments or slow cooling in the temperature range 550ºC -
800ºC, precipitation of carbides takes place. Below 500ºC, precipitation is hindered by the low mobility
of substitutional elements [22].

The most common carbides in ASS are of the type M23C6, although other carbides also precipitate
according to the reference sequence presented in figure 2.1.3-5. The letter M accounts for transition
elements (e.g. Fe, Cr, Ni, W, Mo) and carbides of mixed composition are usually found, depending on
the temperature of the ageing treatment and the composition of the alloy [5]. However, the chromium
carbide has received special attention because of its implications for the corrosion properties of ASS,
and will be discussed in one of the following sections.
The M23C6 carbide is fcc in structure, with a lattice parameter about three times that of austenite, and
grows with a cube on cube orientation relationship [23]:
{100}γ || {100}M23C6
<010>γ || <010>M23C6
Regarding location, carbides are prone to follow the precipitation sequence: random grain boundaries,
non-coherent twin boundaries, coherent twin boundaries and, finally, intragranular dislocations [19, 20,
23]. This phenomenon puts into evidence the existence of a carbon content threshold and an energy
threshold inversely proportional to the interfacial energy of the grain boundary [24].
Upon long ageing treatments, cellular precipitates can form at grain boundaries, together with MC1-X and
M6C carbides [5, 23, 25]. Although they are important for the mechanical properties of ASS, and
particularly to its creep resistance, these precipitates are of no significant relevance to this particular
project and thus will not be treated in detail.

1.3.3. Intermetallics
A number of intermetallic compounds may precipitate in ASS, depending on the alloy composition,
during relatively long ageing heat treatments [15]. These usually involve some degree of partition of
alloying elements, and thus affect the mechanical and corrosion properties. Table 2.3-2 lists some of the
most common phases, and figure 2.1.3-6 shows some experimental observations on the time-to-
precipitation in ASS at 550ºC - 600ºC. The formation and evolution of these secondary phases have
been extensively discussed and remain disputed, although evidence indicates that the presence of δ
ferrite has a strong effect in their occurrence and that they nucleate and grow faster through a
collaborative-eutectoid reaction [26].
The Fe-Cr σ-phase is, perhaps, the most studied intermetallic phase in ASS, and has negative effects in
toughness and corrosion resistance [15]. Increasing contents of Cr, Mo and Si are known to ease
precipitation of σ-phase and the presence of δ ferrite, being richer than austenite in these alloying
elements, provides nucleation sites. Furthermore, the diffusion rate of Cr and Mo is significantly higher
in ferrite than in austenite, thus requiring shorter times and lower temperatures for precipitation of σ-
phase to occur. At the same time, the solubility of carbon in σ-phase is very low, so that this phase
usually precipitates in carbon impoverished regions, i.e. after precipitation of M23C6 carbides [27].
According to calculations done by Sourmail and Bhadeshia [28], the precipitation of σ-phase is more
difficult than M23C6 carbides, and is consequently restricted to high energy sites in the microstructure.
The (η) Fe2M Laves phase (where M usually represents Mo, Nb or Ti) is a hexagonal intermetallic
compound found in minor volume fractions in ASS, and exhibits similar precipitation kinetics to σ-phase,
although there is no general agreement on the temperatures and times required for this precipitation to
take place [25]. Laves phase has been reported as a transient phase, preceding the formation of M6C

carbides [23]. Retained δ ferrite hinders the formation of Laves phase, and the latter shows some
competitive interaction with σ-phase and also χ-phase [26].
χ-phase is a Fe-Cr-Mo intermetallic compound that may precipitate in ASS in minor quantities and after
longer soaking times at relatively high temperatures, typically over 750ºC [23]. Its formation is related to
the presence of M23C6 carbides and δ ferrite in the primary microstructure [29], and it is mainly found in
AISI 316 at high ageing temperatures.
Other precipitates, although of importance to the properties and applications of ASS, have not been
mentioned in this section because of their low incidence in this particular study, and they will be
introduced at a later stage only when necessary. Some examples are: G-phase silicide, Z-phase
carbide, nitrides, phosphides, sulphides, copper and nickel containing intermetallics.
The following section deals with the corrosion properties of ASS, and relates some of the metallurgical
features here presented with their iconic corrosion resistance.
1.4. Corrosion properties of AISI 316
The corrosion resistance is the most important property for ASS, and these alloys were designed and
are usually selected for service under mild to severe operating conditions. A suitable grade of stainless
steel will generally serve well for many years, but the selection of the wrong grade or heat treatment can
lead to catastrophic failures [30]. This is because ASS owe their corrosion resistance to the formation of
a passive film at the surface, which isolates and protects the bulk material from the corrosive
environment. The nature of the passive film is dynamic, and dissolution and repair take place

continuously, although under especial conditions this protective layer may be destroyed, leading to
severe corrosion [2, 31].
The existence and protective role of this oxide film was first proposed by Faraday, but confirmation had
to wait for many years until a suitable method was developed to isolate it and to study it [32-34]. From
then onwards, much research work has been conducted on the nature of this passive layer, and the
properties that different alloying elements impart to it, given that the electronic properties of the film are
believed to play an important role on its stability through ion and electron transport reactions [35, 36]. To
this end, the fundamental explanation is still a matter of dispute, but it is widely accepted that the
availability of oxygen is crucial for the formation of the passive film; chromium is the main and most
important constituent, although minor additions of other alloying elements also have an important effect.
The content of chromium is critical to provide the steel with corrosion resistance, and the minimum
amount required is a function of the operating conditions, namely the type of acid, its concentration and
temperature. As a general rule, the onset of a passive film is found at chromium contents in the order of
12% [37], although 17% to 20% is usually required to impart passivity to ASS in many corrosive
environments [2, 31]. In any case, higher chromium contents do not always improve corrosion
resistance, and the opposite trend may be observed in some acids, for example sulphuric and
hydrochloric.
The effect of nickel in the corrosion properties of ASS depends on the presence and quantity of other
alloying elements, as some kind of synergistic effect with chromium has been suggested [2]. For the
particular amounts and proportions found in ASS, nickel is reported to promote repassivation and

increase the corrosion resistance in reducing and mineral acids, while having a weak but beneficial
effect on pitting corrosion [2, 31, 38].
Additions of molybdenum produce a marked improvement in the resistance of ASS against reducing
acids, pitting and crevice corrosion [2, 31]. Even though molybdenum is not an integral part of the
passive Cr-rich film, it was found to stabilise it, particularly in the presence of chlorides [36]. On the
other hand, ASS with large amounts of this alloying element are prone to segregation and precipitation
of secondary phases and, consequently its use is limited to moderate contents [39].
Nitrogen is beneficial in reducing the segregation of Mo-containing phases and providing further
resistance to pitting corrosion [31]. Silicon, vanadium, tungsten and copper are respectively found to
provide some beneficial effects to ASS under different service conditions [38]. Figures 2.1.4-1 and 2.1.4-
2 show the schematics of the polarisation curve of ASS in sulphuric acid and the effects of different
alloying elements on it.
The corrosion resistance of ASS is defined not only by the content and proportion of alloying elements,
but also by the way in which these elements are dispersed in the microstructure. In this way,
segregation and precipitation of secondary phases play a very important role in determining the form of
corrosion, i.e. general corrosion or some localised attack of the kind of pitting, crevice, intergranular
corrosion, or even galvanic corrosion [31].
Perhaps the most important phenomenon for the corrosion resistance of ASS, and one that has taken
much attention from researchers, is the precipitation of chromium carbides of the form M23C6. The
negative effect is not a product of the carbide itself, but of the depletion of chromium in the area

surrounding the precipitate, where corrosion takes place in a very rapid way [40, 41]. This phenomenon
is usually referred to as sensitisation and may lead to intergranular corrosion and, ultimately, to the
complete failure of the component in service.
In order to avoid sensitisation, the carbon content of ASS is kept at the lowest possible level, at expense
of the mechanical properties, and other alloying elements (Ti, Nb) might also be added as stabilisers,
i.e. to combine with the remaining carbon and form MC carbides instead of the harmful Cr23C6 [2, 38]. At
the same time, heat treatments or slow cooling in the temperature range 550ºC - 800ºC should also be
avoided.
Precipitation of carbides has also been found to depend on the crystallography of grain boundaries, with
random grain boundaries being more prone to precipitate carbides and also some other secondary
phases, as opposed to the coherent twin boundaries [19, 20, 42]. This is a result of the high number of
atoms common to both grains of the coherent twin boundary, which reduces the energy of the boundary
[43]. More recent studies have reported some correlation between the crystallographic texture [44] and
also the type, distribution and connectivity of grain boundaries [45, 46], with the corrosion behaviour of
the alloy.
These models make use of the theory of Coincident Site Lattice (CSL), which classifies the grain
boundaries according to the misorientation of the neighbouring grains and, consequently, according to
the fraction of coincident atoms between neighbouring lattices [47]. This is usually expressed as the
reciprocal density of coincident sites Σ, and boundaries with high fraction of coincident sites, i.e. low Σ
number, are believed to exhibit special properties [48]. In the case of alloys of low stacking fault energy,

Σ3 twin boundaries are the simplest and most prominent ones because of their high number fraction
and length fraction [47, 49].
A grain boundary can be defined by five parameters or, in other words it can be said to have five
degrees of freedom: 3 account for the crystallographic relationship between neighbouring lattices and 2
define the plane orientation of the grain boundary [49]. Therefore, the CSL model is not restrictive
enough inasmuch as it fails to account for the plane orientation of the grain boundary [48, 50].
Consequently, a coincident site relationship between neighbouring lattices does not always imply a
coincident site boundary or special boundary [43]. Nevertheless, the CSL theory is useful to categorise
grain boundaries in view of the relative difficulty to define all five degrees of freedom [50].
Finally, the presence of deformation slip bands and also MnS inclusions in the microstructure can
reduce the corrosion performance of ASS [38]. The latter inclusions are reported to be favourable sites
for pitting. Generally speaking, every discontinuity or weak point in the passive film will be susceptible to
corrosion (figure 2.1.4-3).
H. Brearly, known as the father of stainless steel, used to be called the inventor of the knife that would
not cut. This rather anecdotal comment on the difficulties found in keeping stainless steel knives sharp
is timely when introducing one not so positive aspect of these alloys: their low hardness and wear
resistance.
1.5. Tribological properties of AISI 316
As opposed to corrosion, the wear properties of ASS are moderate, and it is fair to say that ASS are not
usually selected because of their tribological performance (figure 2.1.5-1). However, it is sometimes

difficult to completely avoid sliding or tribological interactions of some kind during service [51, 52].
Furthermore, ASS could be selected because of their corrosion resistance or their non-magnetic nature,
at the expense of the wear performance. In any case, the wear properties of ASS are of interest in order
to select the material correctly and predict its failure.
The phenomenon of wear involves several material properties (e.g. strength, hardness, toughness,
thermal conductivity) and also the operating conditions (e.g. contact geometry, load, sliding speed,
temperature). Therefore, it can be said that wear poses a problem with a relatively high level of
complexity. The models and theories proposed in the literature are usually limited to a relatively small
range of materials and conditions, and the diversity of theories and terminology can be misleading.
For the sake of clarity, and at the expense of accuracy, the different wear mechanisms will be
introduced by using the wear map shown in figure 2.1.5-2 [53-55]. The normalised pressure and
normalised velocity are respectively defined as:
~ F
F= (2.1-5)
An ⋅ H
v ⋅ ro
v~ = (2.1-6)
a
where F is the applied load, An is the contact area, H is the material hardness, v is the sliding velocity, ro
is the radius of the contact area and a is the thermal diffusivity. The range of conditions relevant to this
project is that of medium-low velocity and medium-high load (i.e. top left quarter of the map in figure
2.1.5.2).

The wear of ASS has been studied by a number of authors, under different testing conditions [52, 56-
61]. There is a good degree of coincidence in the experimental results and observations, although not
so with regard to the fundamental explanation of the wear mechanisms. In general, the poor tribological
properties of ASS are associated with damage by galling or seizing [56], especially at high loads and
low sliding speeds, so that it can be said that wear of severe nature takes place by adhesion [62, 63].
In this wear mode, junctions are formed between the sliding elements, at the interacting asperities, and
subsequently deformed until rupture occurs, producing very rough wear tracks [64]. In this way, material
is transferred from one of the contacting surfaces to its counterpart throughout sliding (figure 2.1.5-3).
Furthermore, plastic flow is not confined to the interacting asperities but it extends towards the
subsurface. This leads to the nucleation of cracks, which propagate parallel to the surface and are
ultimately responsible for the detachment of plate like wear debris particles of large size, through a
mechanism called delamination wear [65].
At low temperatures, below Md, the strain produced at the surface and subsurface of ASS sliders is
sufficient to induce martensitic phase transformation, and it is well established that the formation of
martensite has a significant effect in the wear phenomenon [52, 56, 57, 66]. The thickness of the work
hardened and martensite layer depend on the material and the sliding conditions, namely load and
sliding speed.
Some opposing effects have been reported for this hardened layer, based on two different mechanisms.
On the one hand, martensite is said to increase the hardness of the substrate and, consequently, its
wear resistance [57, 62, 67]. On the contrary, other authors have reported that the austenitic substrate,
even after work hardening, is not strong enough to support the hard but brittle martensite surface layer,

leading to a high rate of fracture and formation of abrasive debris particles [56]. In such a scenario, the
resilience and toughness of the material are of significant importance, and the ratio of hardness to
elastic modulus has been reported to be a more appropriate index than the mere hardness, to rank the
wear resistance [68, 69]. Best tribological performances have been reported for combinations of high
surface hardness and relatively low elastic modulus, to reduce the tendency to plastic deformation and
reduce the mismatch of properties, while keeping deformation within the elastic range.
Mild wear conditions are found at some higher sliding speeds and lower loads, as can be seen in the
wear map in figure 2.1.5-2. The reduced wear rates are associated with the formation of a flat and
smooth protective oxide layer on the surface [57-60], and the onset of a mechanism called oxidational
wear [63]. A competition is established between the removal of the oxide layer through abrasion or
flaking; and the reaction and passivation of the fresh metal surfaces exposed to the environment [70].
The former depends mainly on the load, whilst the latter is a function of the temperature and,
consequently, the sliding speed. Under the right sliding conditions, a thin and tough oxide layer covers
the surface uniformly and exerts good resistance to wear [57].
The ductility and resilience of the oxide layer are important to accommodate the deformation of the
substrate [63]. In addition, the hardness and the elastic properties of the underlying material are critical
to provide the necessary support to the layer of oxide. Under stable oxidational wear conditions, the
oxide layer grows up to a critical thickness, at which it becomes unstable, and it finally flakes off by the
propagation of fatigue cracks.
The stoichiometry of the oxide depends on the environment and the temperature of formation, i.e. the
temperature at the sliding asperities, and its effect on the wear phenomenon is of significance [58]. At

low temperatures, below 300ºC, α-Fe2O3 forms, whilst at temperatures between 450ºC and 600ºC Fe3O4
becomes stable and over 600ºC FeO is found [71]; in the presence of moisture, these oxides may also
form hydroxides [60, 72]. Once again, there are some controversial reports on the effect that each
specific type of oxide has over wear rates and friction, but oxides are generally associated with mild
wear regimes and detachment of fine debris particles [57, 59].
With regard to friction force, coefficients in the range 0.4 to 0.7 have usually been reported for a wide
range of sliding conditions. An average coefficient of friction of 0.5 can be considered with fairly ample
agreement [56, 60], although some variations and fluctuations in the friction force have also been
mentioned [52]. The fluctuating nature of the friction force is well known [73], and it has been associated
with the interaction of surface asperities [74], wear mode transitions, and formation, trapping and
detachment of large wear debris particles [75]. It is interesting to note that discontinuities in the plastic
deformation at the subsurface, such as twinning and phase transformations, would also yield
fluctuations and variations in friction [56].
This succinct summary of the tribological properties of ASS was intended to provide a reference frame
and introduce the basic principles of wear and friction under dry sliding in air. It is clear that the poor
tribological performance of ASS represents a serious limitation for many applications, which demand
excellent corrosion and wear resistance. Other stainless steels or non-ferrous alloys will continue to
develop and might fill part of this gap, although this is usually achieved at the expense of toughness,
corrosion resistance, ferromagnetism or cost. Surface engineering offers an alternative way to improve
the tribological properties of ASS at the surface level, while keeping the traditional benefits of this
material.

2. Surface engineering
2.1. Introduction and basic concepts
The wide use of surface treatments and coatings to combat wear was foreseen many years ago, based
on the fact that the mere use of wear resistant bulk materials can be inappropriate and expensive [76,
77]. Furthermore, the increasing level of understanding of the importance of the surface properties and
surface condition to the most common failure modes, i.e. wear, fatigue and corrosion, led to the
recognition of surface engineering (SE) as a key technological area [78-80].
Several definitions have been proposed, usually implying the application of processes or treatments to
deliberately modify the surface of engineering components, in order to attain adequate material
properties for a given application, thus providing a cost effective enhancement in performance [81, 82].
This definition involves the concept of fitness-for-purpose [83] and it is generally accepted that SE can
offer benefits such as [84]:
Enhanced functional performance and higher productivity
Use of cheaper substrate materials
Provide flexibility to match substrate and surface properties for a particular application
It is of paramount importance to consider both the surface and the substrate when designing or
selecting a SE treatment, as it has been pointed out by many authors [76-78, 82, 83]. The concentrated
loads developed during the contact and slide of rough surfaces are of significance in tribological
applications [85]. The strength of the substrate and the thickness of the coating or hardened layer define
the load bearing capacity and fatigue response of the system, as shown in figure 2.2.1-1 [86-88]. A
complete understanding of the behaviour of the substrate/surface system under the operating conditions
is, thus, crucial.

SE can be described as an old and well known practice [83], and some examples of instructions for
tempering and case hardening of metal weapons and tools have been quoted in the literature, dating
back to 1400 BC [81]. The innovative aspect of SE is the design approach, and the increasing
awareness of the importance of the surface properties and the surface condition to the performance of
the interacting surfaces [78, 84]. In view of the increasingly demanding operating conditions and the
requests to reduce production costs, many industrial sectors have turned their eyes to SE, making this a
blooming area of technology.
The variety of SE treatments can be appreciated in figure 2.2.1-2. The ever wider range of options, and
the absence of a comprehensive system for selection constitutes a great challenge for design engineers
and the choice of a particular treatment is usually based on previous empirical experience rather than
on a detailed or analytical study [76, 78, 89]. For the purpose of this review, the SE treatments will be
classified, very broadly, into three groups [90]:
Those which coat the substrate: PVD, CVD, thermal spraying, etc.
Those which modify only the structure of the substrate: induction hardening, flame hardening
and shot peening.
Those which modify the chemical composition and the structure of the substrate:
thermochemical, ion implantation, etc.
The ones of significance to this project are the thermochemical or diffusion hardening processes, and
they will be treated in further detail in the next section.
Finally, the environmental impact of SE must be taken into account, in view of the increasingly stringent
regulations, if not for our own sake. If the energy content of one particular material is taken as a

measure of its environmental friendliness (figure 2.2.1-3), it is evident that any additional process
applied to it would increase its environmental footprint. However, if the increase in performance is
significant enough, the trend is reversed. SE treatments can increase the life span of the components,
reduce their size and weight, decrease energy losses associated with friction, minimise or even
eliminate the use of polluting lubricating oils, among other environmental benefits [91].
2.2. Thermochemical and diffusion surface engineering treatments
Thermochemical treatments, sometimes referred to as case hardening or cementation, are based on the
modification of the chemical composition of the substrate material. These treatments can be succeeded
by a change in the structure through heat treatment. The formal definition available in BS EN
10052:1994 reads as follows [92]:
Thermochemical treatment: Heat treatment carried out in a medium suitably chosen to produce
a change in the chemical composition of the base metal by exchange with the medium.
In the case of diffusion treatment, the definition in that same standard is:
Diffusion treatment: Heat treatment or operation intended to cause the diffusion towards the
interior of the ferrous product of elements previously introduced into the surface (for example,
following carburising, boriding or nitriding).
From these definitions it becomes clear that two main factors will govern the process, namely: the
exchange or absorption reaction with the medium, and the diffusion in the metal [93]. As it is illustrated
in figure 2.2.2-1, the medium will determine the way in which the diffusing elements are delivered to the

metal surface. A number of different media are available (solid, liquid, gas and plasma), and a detailed
account of the media used for carburising will be given in a following section.
Once in the metal, the transport of the absorbed substance takes place by diffusion, and follows Fick’s
laws:
∂C
J = −D (2.2-1)
∂x
∂C ∂ 2C
=D 2 (2.2-2)
∂t ∂x
where J is the flux of diffusing substance, D is the diffusion coefficient, and ∂C/∂x is the concentration
gradient [93, 94]. Therefore, the transport of the substance in solution is driven by its concentration
gradient and the diffusion coefficient which, at the same time, depends on the temperature, the chemical
composition and phase structure of the substrate. For a given alloy, kept at constant temperature in a
medium with a consistent concentration of the substance of interest, the case depth will only depend on
the time, according to equation (9):
x = a (Dt )
1/ 2
= Kt 1 / 2 (2.2-3)
where x is the case depth, a is a constant, D is the element diffusivity, t is the treatment time and K is a
factor determined by a and D [93]. Higher treatment temperatures yield the same case depth in shorter
time, although there are technical limitations related with life of the furnaces, and metallurgical
considerations regarding the side effects of keeping the substrate material at high temperatures [94].
Consequently, diffusion treatments are slower when compared to other surface deposition techniques
[77], and treatments as long as 72 hours are common practice in industry. On the other hand,

thermochemical treatments produce smooth case-core interfaces, which are beneficial for not only the
wear and fatigue performance, but also the load bearing capacity [95].
The next section focuses on the application of thermochemical treatments on austenitic stainless steel
substrates.
2.3. Low temperature thermochemical surface engineering of austenitic stainless steels
2.3.1. Rationale of low temperature treatments
As it has been mentioned in a previous section, the chemical composition of ASS makes them fully
austenitic up to room temperature, and thus no phase transformation hardening takes place upon
quenching. Consequently, SE treatments are an interesting alternative way to increase the surface
hardness and improve the wear resistance. However, SE of ASS has traditionally been considered bad
practice [30], as it poses two main problems: the passive oxide film and the precipitation of chromium
carbides [96].
The passive chromium oxide film on ASS is stable under a wide range of conditions (figure 2.2.3-1) and
isolates the substrate from the environment. This effect has been of interest for ASS components
exposed to carburising gas mixtures, either in service [97, 98] or for SE purposes [99]. In the latter case,
the oxide layer impairs diffusion of the hardening elements and, consequently, needs to be removed by
applying some sort of surface activation process prior to the SE treatment [100, 101].
Furthermore, traditional SE treatments are conducted at high temperatures, around 500ºC - 600ºC in
the case of nitriding, and 900ºC - 1000ºC for carburising [102, 103]. At these temperatures, and with
increasing availability of nitrogen and carbon from the hardening medium, profuse precipitation of

chromium nitrides and carbides occurs, leading to a marked deterioration of the corrosion resistance of
ASS. However, low temperature SE diffusion treatments with nitrogen and/or carbon have been
reported to increase the surface hardness without affecting or even improving the corrosion resistance
[103, 104].
It is nowadays widely accepted that hard, wear and corrosion resistant surface layers can be produced
on ASS by means low temperature nitriding and/or carburising in a number of different media (salt bath,
gas or plasma), each medium having its own strengths and weaknesses [105]. In order to retain the
corrosion resistance of ASS, these processes are typically conducted at temperatures below 450ºC and
500ºC, for nitriding and carburising respectively (figure 2.2.3-2). The result is a layer of precipitation free
austenite, supersaturated with nitrogen and/or carbon, which is usually referred to as S-phase or
expanded austenite (EA) [105-109].
2.3.2. Metallurgical aspects of expanded austenite
There is general agreement in the literature regarding the thickness and the composition of EA layers.
Maximum thicknesses in the order of 20 μm and 50 μm have been reported for nitriding and carburising
respectively [107], with 20 at.% to 30 at.% of N and 5 at.% to 12 at.% of C correspondingly [109]. In the
case of nitriding, the layer shows a steep gradient in composition (figure 2.2.3-3), with the associated
abrupt change in properties, whilst the composition depth profile for the carburised layer is smoother
[96, 105, 109]. The deviation of the carbon-depth profile in figure 2.2.3-3 compared to the typical profile
shown in figure 2.2.2-1 is attributed to a variation of the diffusion coefficient with the carbon content
[110].

On the other hand, there has been a strong disagreement with regard to the crystallographic structure of
these carbon and nitrogen supersaturated layers [111-115]. The contradiction arises from a genuine
difficulty in the identification of the X-ray diffraction (XRD) patterns, ascribed to the lattice strains and
high density of crystallographic defects intrinsic to this layer of material. To this end, it is generally
accepted that the so called S-phase is an integral part of the substrate with crystalline structure [111,
114]. The evidence indicates that this layer is single-phased, with the same fcc crystal structure of the
parent austenite, although distorted as a result of a high content of interstitial elements in solution [112,
116]. Nevertheless other crystal structures have not been completely disregarded.
With regard to alloying elements, chromium has been considered crucial for the formation of EA, due to
the very high chemical affinity with carbon and nitrogen [101, 106, 109, 117]. Therefore, interstitial C
and N show a high probability to stay in the octahedral interstices of the fcc lattice, surrounding Cr
substitutional atoms, which form trap sites of potential energy [101]. Molybdenum also seems to be
beneficial to the kinetics of carburising, by delaying the precipitation of chromium carbides and thus
allowing higher treatment temperatures [118], and by expanding the octahedral interstices in the fcc
lattice [119].
From the thermodynamic point of view, EA is metastable and it will decompose into the stable austenite
and carbide or nitride phases upon heat treatment [106, 108, 116, 120]. The incubation time for
decomposition is temperature dependent, and nitrogen EA decays faster than carbon EA (figure 2.2.3-
2), so that for prolonged service time, maximum operating temperatures in the order of 200ºC and
300ºC should be considered respectively. This metastable equilibrium or paraequilibrium is based on
the fact that at the low temperatures at which the treatment is conducted, carbon and nitrogen exhibit
diffusion rates significantly higher than the almost immobile substitutional elements, Cr and Ni. Under

such conditions, the precipitation of carbides and nitrides is suppressed, or delayed until large amounts
of carbon and nitrogen are in solution [110, 117].
Detailed studies and observations with transmission electron microscopes (TEM) have revealed the
precipitation of fine nitrides and needle-like carbides, especially in the outmost layer or close to
structural defects in the microstructure [116, 121, 122]. Calculations of the volume misfit indicate that
the strain energy associated with the precipitation of carbides contributes to keep the carbon in solution,
although at high levels of supersaturation and expansion of the austenite cell, this energy barrier is
significantly reduced [123].
The reported nitrides were of the MN type, while the carbides were of the M5C2 χ-kind (where M stands
for metal and is most commonly Cr). In both cases, precipitation seems to follow a very specific and
consistent orientation relationship with the austenitic phase [116, 121]:
{001}γ || {001}CrN
<001>γ || <001>CrN
{111}γ || {001}M5C2
<211>γ || <010>M5C2
Moreover, composition studies conducted on a scanning transmission electron microscope showed
partitioning between the carbide and the austenitic phase of not only carbon, but nickel as well [123].

Summarising, the precipitation of nitrides or carbides takes place only after a relatively high level of
supersaturation and expansion of the austenite has been reached, thus reducing the volume misfit
strain energy barrier [123]. At the same time, the observed orientation relationship enables precipitation
of needle-like carbides with highly coherent interfaces, minimising the long range transport of misfit
dislocations and substitutional elements, mainly nickel.
2.3.3. Properties and applications of expanded austenite
Tensile tests have shown only minor differences between the untreated and treated ASS, some of the
differences arising from the thermal cycle rather than the SE treatment itself [110, 124]. These
differences can be summarised as a small reduction in the yield strength and in ductility, with a minor
increase in the ultimate strength and elastic modulus; and they were attributed to the existence of high
compressive residual stresses on the treated layer, and to a strain ageing effect produced at the
treatment temperature.
The high compressive residual stresses present on the EA layers predicted obvious increases in the
fatigue life and, in general, improvements of about 25% have been reported [125]. This is the result of a
change in the failure mode, as the hard EA layer suppresses the alternating slip deformation at the
surface [110, 124]. Consequently, the crack initiation site moves inwards, to the interface between the
substrate and the EA layer, which can be explained by the strength-applied stress diagram in figure
2.2.1-1 [126]. It must also be noted that a minor increase in the notch sensitivity has also been reported
for the low temperature carburised ASS [127].
The improvement in wear resistance is perhaps the most outstanding feature of EA. The degree of
improvement depends on the sliding conditions, but volume losses between one and two orders of

magnitude lower than the untreated ASS are commonly reported for dry sliding [96, 125]. This
improvement is attributed to the increased surface hardness, with a typical ratio 4:1 compared to the
untreated ASS [128]. The EA layer prevents the surface from undergoing plastic deformation, and
changes the wear mechanism from adhesion and abrasion, to a mild oxidational wear regime [128,
129]. However, under heavier loads, deformation of the subsurface occurs and leads to catastrophic
failure, through propagation of subsurface cracks and spallation of the EA layer [130]. In this way, the
carbon EA layers, being thicker and tougher than their nitrogen counterparts, show some advantage.
With regard to corrosion, the results vary significantly depending on the testing conditions. Surprisingly,
most researchers found that low temperature nitriding and/or carburising do not harm the corrosion
resistance of ASS, or even improve it. No conclusive explanation has been found for this improved
corrosion behaviour, although it is clear that the benefit stands as long as nitrogen and carbon remain in
solution and EA is free of precipitates [120]. In NaCl solutions, it is generally reported that EA remains
passive under similar or wider range of potential compared to the untreated ASS, carbon EA showing a
marginal advantage over nitrogen EA [96, 131, 132]. Similar or slightly higher initial current densities
have usually been measured on EA, together with the absence of pitting potential, in contrast to what is
usual for ASS [96, 125, 133]. Regarding repassivation, the evidence indicates that the passive film heals
slower on EA than on ASS [132, 134].
This attractive combination of properties has caught the attention of both research and industrial fields,
which is reflected in an increasing number of technical papers, reports, patents and processes. The
applications include hydraulic pump components, valves, ball bearings, ferrules, etc. [135-143]. In the
next section, some common processes to produce EA on ASS will be presented.

2.4. Common processes to produce expanded austenite
As it was previously mentioned, there are a number of different media capable of delivering carbon or
nitrogen to enrich the surface of steel components, although not all of them are suitable for treating ASS
or producing EA. Methods such as pack carburising and salt bath carburising or nitriding strongly
depend on temperature to control the process driving reactions, and their effectiveness is low at the
temperatures required to produce EA (T < 500ºC), especially in the case of carburising [88, 93].
Moreover, they have been widely superseded by gas media because of technical and environmental
reasons.
Gas carburising with endothermic gas is, nowadays, the dominating carburising technology [144] and it
has been successfully employed to produce EA [145, 146]. The main chemical reactions are as follows
[93, 94]:
CH 4 ↔ (C ) + 2H 2 (2.2-4)
2CO ↔ (C ) + CO2 (2.2-5)
CO + H 2 ↔ (C ) + H 2O (2.2-6)
whilst the atmosphere control reactions are:
CO 2 + H 2 ↔ H 2O + CO (2.2-7)
CO 2 + CH 4 ↔ 2CO + 2H 2 (2.2-8)
H 2O + CH 4 ↔ CO + 3H 2 (2.2-9)
The carburising potential of the atmosphere (KC) is usually controlled by reaction (2.2-6) according to
the following equation:

p CO p H 2
KC = (2.2-10)
p H 2O
where pCO, pH2 and pH2O are the partial pressures of each of the gases involved in the reaction.
There is some degree of secrecy about the available commercial processes to produce EA, but the vast
majority of them are based on gaseous atmospheres containing CO [135, 145, 147]. The results are
satisfactory, and the only drawback of these processes is the need for a prior surface activation to
remove the passive oxide film, which is usually accomplished by using halogenated gases [100, 147,
148]. The low working pressures associated with vacuum carburising are known to remove the oxide
layer from the treated components, although they require high temperatures to do so (900ºC to 1100ºC)
and to activate the process reactions, i.e. thermal decomposition of the hydrocarbon gas under the
catalytic effect of the hot steel surface [93, 149-152]. Another alternative is plasma SE, which removes
the passive oxide film from the surface of ASS components through the sputtering action of highly active
species present in the plasma [88]. Being the subject of this project, they will be treated in further detail
in the next section.
2.5. Plasma surface engineering
Plasma surface engineering (PSE) is based on the abnormal glow discharge phenomenon that takes
place on parts subjected to cathodic potential (several hundred volts), while being immersed in a low-
pressure gas atmosphere (rough-medium vacuum) [153-157] (figure 2.2.5-1). Active species (i.e.
excited or ionised atoms and molecules) are generated within the plasma and accelerated towards the
cathodic worktable, where the parts to be treated are placed. While most of the energy involved in this
process is released in the form of heat, a small part of it allows nitrogen and/or carbon species to be
transferred to the solid state, through mechanisms that remain unclear.

It is custom to compare this plasma technology with gas or vacuum diffusion processes, although in
PSE the reactions are under electric control, and the conventional equations to calculate the potential of
the atmosphere do not entirely hold [152, 158]. The number of process variables increases:
temperature, time, gas composition, pressure and flow rate, voltage, current, boost-diffusion cycle time
and ratio, just to mention some. This larger number of relatively independent variables makes it more
difficult to control and optimise the treatment, but also permits a higher degree of freedom when
selecting the processing conditions.
As previously stated, the process variables are not completely independent of each other, and their
interactions are of significant importance. The gas pressure affects the mean free path of the active
species in the plasma [159, 160], and their kinetic energy is proportional to the acceleration produced in
the cathode fall, i.e. the applied voltage [154, 155]. These two variables define, to some extent, the
interaction between plasma and substrate, and the relative importance of some of the phenomena that
take place during the process: sputtering, edge effect and ion implantation [161].
Plasma nitriding (PN) is usually performed in N2-H2 gas mixtures or NH3. On the other hand, CH4-H2
mixtures are mainly used for plasma carburising (PC) purposes, although other carbon containing
gases have proved to be useful in some cases [162]. The dilution of the gas is one of the variables that
determine the flux of C or N transfer into the solid state, i.e. the rate of saturation of the surface [163].
Hydrogen additions are convenient for surface depassivation, especially when treating ASS. Moreover,
the hydrogen content of the gas mixture also increases the tolerance of the process to possible air
leaks in the chamber [164]. Small amounts of argon might be added to increase the sputtering effect
and for surface activation [165].

The sputtering phenomenon is a very efficient heating mechanism, and it depends on the voltage and
current density, the gas mixture and gas pressure, and even the shape of the components [166]. For
treatments conducted at temperatures below 570ºC, sputtering can be the only source of heat, whilst
additional heating is often required or convenient for higher temperatures [155, 167]. This is because in
order to reach high temperatures by means of sputtering only, very high electric potentials are required,
making the process unstable (arcing transition). However, it was found that much lower power densities
are required for the activation of the treatment reactions, while the temperature can be reached using
electric resistors, cathodic heaters or hollow cathodes [168, 169].
Decoupling temperature from electric plasma activation gives more freedom in the selection of the
treatment conditions and better process stability and control [170-172]. Even though the activation
provided by plasma during PSE is obviously responsible for the high rates of carbon and nitrogen mass
transfer to the surface of the sample, the mechanisms involved are still not clear, and the models
proposed in the literature have been severely disputed. Once the surface content reaches the
saturation limit, the diffusion of N and C into the bulk material is a function of temperature, time and
chemical driving force [163]. Depending on these three parameters, the final thickness of the alloyed
layer and concentration gradient of the diffusing elements can vary from a few micrometers up to
several hundreds of micrometers.
Direct current (DC) glow discharge thermochemical processes experienced a rapid uptake in industry in
the 1970s and 1980s [161]. The advantages over conventional thermochemical treatments include:
shorter cycle times, higher energy efficiency, lower gas consumption and environmental friendliness,
just to mention some [156, 163, 170, 173, 174]. However, the higher equipment costs, the lack of
thorough understanding of the process and such intrinsic problems of DC glow discharge plasma as

arcing, hollow cathode and edge effects were found to be difficult to solve, and thus a further spread of
this technology has virtually stopped.
Moreover, the homogeneity of the temperature within the chamber was not satisfactory for some
applications. Different methods were attempted in order to improve this aspect, making use of external
heat sources like electric resistors or cathodic heaters [168]. These are metal sheets or meshes,
subjected to cathodic potential, which are heated by the ionic bombardment and radiate heat to the rest
of the chamber, thus heating the colder parts of the workload. A further improvement of this concept,
together with the idea of post discharge plasma, became a novel plasma technology in 1999, named
active screen. Active screen plasma (ASP) shows great potential to overcome the problems associated
with DC plasma technology [175].
2.6. Active screen plasma technology
Among the plasma processes alternative to the DC technique, ASP is of particular interest due to the
simplicity and effectiveness of its concept. In a conventional DC furnace, the worktable is negatively
biased with respect to the wall of the chamber, which is earthed and plays the role of the anode in the
electric circuit. If no supplementary heating elements are used, the workload needs to be subjected to
relatively high electric potentials, in order to reach the treatment temperature by means of sputtering.
The high electric potentials applied imply that the working condition moves closer to the arcing transition
point in figure 2.2.5-1, and renders the treatment unstable, especially when the components are not
completely free of grease, oxide scale or any other contaminant.
Moreover, components with complex geometries and of different sizes may not be heated uniformly,
because of the distortion of the electric field in proximity of sharp edges [176]. The distortion of the

electric field affects the plasma and the plasma surface interactions, such as ionisation and sputtering,
so that parts with small radius of curvature treated in DC furnaces are prone to the so called edge
effect. The local temperatures developed at the edges can be much higher than in the rest of the
component, causing changes in metallurgical structure and mechanical properties.
At the same time, hollow cathodes are the third type of defects frequently encountered in DC plasma
treatments, and blind holes or dense work loads are vulnerable to this effect [169]. Hollow cathodes
take place when two surfaces exposed to the plasma are separated by a certain distance, depending
on the gas mixture, pressure and applied potential. These process variables define the thickness of the
plasma sheath, as it will be explained in the next section. The overlapping of the plasma sheaths
produces a peculiar electric field that traps electrons, which oscillate between the cathodic surfaces,
increasing the ionisation events and producing a local increase in current density, with the consequent
increase in temperature.
In the case of the active screen technology, the workload is surrounded by a mesh, which plays the role
of the cathode (figure 2.2.6-1). The purpose of the mesh or active screen is twofold [177]:
It radiates heat to the work load: the cage, being the cathode of the circuit, it is subjected to
severe sputtering that increases its temperature; heat is thus transmitted to the workload by
radiation and, to a lesser extent, by convection.
It generates active species, principally excited neutral atoms and molecules, which are believed
to be important for the treatment.
The worktable is electrically insulated, or subjected to a low negative bias to ease the flow of active
species to the components [175]. In this way, sputtering does not take place on the surface of the

sample but on the mesh, and the workload is heated by radiation from the screen so that the
temperature is more uniform and stable. Thereby, defects associated with direct exposure of the
workload to highly negative potentials are reduced or eliminated. In practice, the AS technique has
proved to be less sensitive to grease and rust on the treated parts [178]. From the aesthetic point of
view, better surface qualities can be obtained, with complete absence of edge effects [179]. Finally, the
local increases in temperature are reduced, producing more even hardening effects and properties
[180].
Apart from its technological importance, AS has raised the unresolved issue of the nitriding and
carburising mechanisms. Much work has been done on AS plasma nitriding (ASPN) in laboratory scale
units, and it was concluded that the principal mass transfer mechanism involved sputtering of iron from
the mesh, reaction of the iron atoms or particles with the active nitrogen in the plasma, and deposition
of the iron nitrides on the worktable with subsequent decomposition and diffusion of free nitrogen [181-
183]. However, the experience on industrial scale units has shown that other mechanisms and effects
must be involved in the process [184, 185]. Furthermore, little work has been conducted up to date on
active screen plasma carburising (ASPC).
It is evident that the mechanisms of plasma treatments pose a difficult challenge, which involves not
only metallurgical aspects but also plasma-surface interactions and plasma physics. Therefore, the next
section will introduce some basic but useful concepts of plasma physics and the plasma diagnostic
techniques.

3. Fundamentals of plasma physics
3.1. Plasma
Plasma is usually known as the fourth state of matter and its inception requires a significant amount of
energy, enough to break some atoms and molecules down into positive and negative particles, i.e. ions
and electrons [186]. The amount of charged particles is balanced, so that the system remains
electrically neutral. Contrary to the other phase changes, the transition of matter to the plasma state
takes place gradually over a wide range of conditions, leading to different degrees of ionisation [187].
The energy required to ionise a gas can be applied to the system in the form of heat, although this is
impractical due to the extremely high temperatures involved [188]. On the other hand, cold plasma can
be produced by means of electric discharges, radio frequencies or microwave excitation of gases.
The study of electric discharges through gases dates back to the 18th century and involves famous
researchers such as Faraday, Crookes, Thomson, Langmuir and Stark, just to mention some [186].
Although gases are good insulators under standard atmospheric conditions, they undergo ionisation
when a strong electric field is applied, thus becoming electrically conductive [189]. A small fraction of
charged particles from cosmic or natural radiation is normally present in the system. These particles are
accelerated by the electric field and acquire sufficient energy to collide inelastically with gas molecules,
ripping electrons or attaching to them to form positive and negative ions, respectively. Direct electron
impacts can also excite the molecules to energy levels higher than the ground state but below the
ionisation threshold.
Relatively few collisions occur in a cold plasma formed at low pressure, thus the system is not in local
thermal equilibrium (LTE) [187]. This means that some highly energetic (fast or hot) particles coexist
with others significantly less energetic (slow or cold) ones. The non-LTE is one of the most attractive

aspects of cold plasma and allows physico-chemical phenomena to take place in a wide range of
conditions, far from equilibrium, depending on the gas composition, pressure, electromagnetic field,
configuration and temporal behaviour of the discharge or excitation method.
Electrons are significantly lighter than neutral molecules or ions and, consequently, they are highly
mobile. They respond faster than ions to fluctuations in electric and magnetic fields, and acquire higher
energies. Even though most applications rely on the kinetics of ions, electrons are the primary agents in
a plasma and their energy distribution is of significant importance [187, 190]. The energy or velocity of
electrons is usually described by a Maxwellian distribution of the form:
3
⎛ me ⎞ 2 2 ⎛ m v2 ⎞
f (v ) = 4πne ⎜⎜ ⎟⎟ v exp⎜⎜ − e ⎟⎟dv (2.3-1)
⎝ 2πk BTe ⎠ ⎝ 2k BTe ⎠
where f(v) is the velocity distribution function according to Maxwell, ne is the electron density, me is the
electron mass, kB is the Boltzmann constant, Te is the characteristic electron temperature and v is the
velocity [190]. Equation (2.3-1) represents a distribution where most electrons (bulk) have relatively low
energies, whilst there is a small fraction (tail) of highly energetic electrons (figure 2.3.1-1).
The density of electrons, or other charged particles, is commonly described by the Boltzmann equation:
⎛ e ⋅φ ⎞
ne = n0 exp⎜⎜ ⎟⎟ (2.3-2)
⎝ k BTe ⎠
where ne is the electron density in any position of potential Φ, n0 is the electron density at a point of zero
potential, e is the elementary charge, Φ is the potential at the position of interest, kB is the Boltzmann
constant and Te is the electron temperature [191].

3.2. Electric breakdown
The electric brakedown of a gas at low pressure involves several steps, as it can be seen from figure
2.2.5-1. In the first regime, the gas is a good insulator and only the charged particles from background
radiation carry a very small current [192]. When increasing the voltage, the current increases mainly
through acceleration of these charged particles, until a saturation value is reached, depending on the
gas composition and the pressure. If the voltage is raised further, the electrons gain sufficient energy to
collide with the gas molecules inelastically, producing more electrons in an avalanche effect. This
phenomenon defines the beginning of the Townsend discharges.
If the voltage is increased further, breakdown occurs and the current increases whilst the voltage can be
reduced markedly. The electric breakdown of a gas is an irreversible process. The ion bombardment on
the work table releases secondary electrons [190, 192], which subsequently multiply through the
forementioned avalanche effect, thus increasing the availability of charge carriers considerably. This
stage receives the name of normal glow discharge, due to the luminous phenomenon observed on the
cathode (emission of light from the decay of excited and ionised atoms or molecules). The current
density remains constant and any increase in current is a consequence of an increase in the area
fraction of the cathode covered by the glow discharge [193].
Once the cathode is completely covered by the glow, a new discharge regime begins, named abnormal
glow discharge. This is characterised by an increase in voltage with increasing current, the latter being a
consequence of a higher current density as the whole surface of the cathode is already involved in the
discharge [192, 193]. It is in this regime that PSE treatments are conducted, thus ensuring that all the
surface of the cathode (i.e. all the components) are exposed to the glow and to the plasma-surface
interactions. The selection of the current density, within the abnormal glow discharge range, depends on

the contribution ion bombardment makes to heating the cathode, and is limited by the onset of electric
arcs. Arcing involves thermal emission of electrons from hot areas of the cathode, most frequently sharp
asperities, although it also occurs on non-conductive pollution or dirt by the accumulation of electric
charge [189, 190].
According to Paschen’s law, for a given gas and electrode material, the breakdown voltage is a function
of the pressure p and the distance between the electrodes L [192]. This correlation is illustrated in figure
2.3.1-2. On the left side of the minimum point (pL < pLmin), low pressure insulation occurs as a result of
the low density of gas molecules and low frequency of ionising collision; whilst on the right side of the
minimum point (pLmin < pL) high pressure insulation is a consequence of the higher energy losses
experienced by electrons and ions in frequent collisions, mainly with neutral gas molecules [189]. Thus
pLmin can be understood as the combination of pressure and distance between electrodes that yields the
highest probability of ionisation and the largest amount of charge carriers.
3.3. Structure of the glow discharge
When a direct current (DC) glow discharge forms between two electrodes, the potential difference is
concentrated close to the cathode, and several different regions are observed (figure 2.3.3-1) [187]. The
first region in front of the cathode is the Aston dark space, a thin layer with a high density of electrons
and very strong electric field, where electrons are still being accelerated and have not yet reached
energy levels high enough to produce inelastic collisions with atoms and molecules, thus making this
region appear dark [157]. Immediately next to the Aston dark space is the cathode glow, with a relatively
high density of ions and, in some cases, excited atoms sputtered from the cathode, which account for
the observed glow. The following is a relatively dark region called cathode dark space, although it is also

referred to as Crookes or Hittorf dark space. The electric field is moderate, and the space charge
becomes positive as a consequence of the higher concentration of ions.
These regions are not always distinguishable and, in some cases, one of them may mask the others
[157, 192]. In general, the space between the cathode surface and the end of the cathode dark space is
called cathode region or sheath [187]. The difference in potential is mostly concentrated in this part of
the discharge, and the thickness of the sheath will adjust itself to pLmin, following Pashen’s law [157].
The electrons are accelerated across the sheath and acquire energy levels high enough as to excite
and ionise gas molecules in the neighbouring area, called the negative glow, or even beyond.
The negative glow is relatively thick compared to the sheath, and is the brightest region of the
discharge. Because of the high density of ions, the negative glow has a positive space charge, and the
electric field in this region is relatively weak. The glow is more intense on the cathode side, where
electrons are energetic enough to produce excitation and ionisation, and fades away towards the anode
as the electrons slow down due to frequent collisions [157, 187]. The drop in the energy of electrons
reduces the ionisation and excitation events and gives rise to another region, called Faraday dark
space. The space charge in this region is small and the electric field is slightly negative.
The remaining space between the electrodes corresponds to a region of uniform glow called the positive
column [157]. If the distance between electrodes is increased, the positive column lengthens while all
the rest of the regions remain unchanged [192]. The electric field in the positive column is slightly
negative and uniform to lead the electrons towards the anode, and the space charge can be considered
quasi-neutral [187, 194]. Approaching the anode, a luminous region may be seen, called the anode
glow, and immediately next to it a dark zone named anode dark space or anode sheath. The latter is the

result of the accumulation of electrons from the positive column next to anode, giving this region a
characteristic negative space charge [157].
This brief summary on DC glow discharges serves as an introduction to the plasma diagnostic
techniques of interest to this project, namely optical emission spectroscopy (OES) and electric probes,
which will be explained in the following sections.
3.4. Plasma diagnostics
Plasma diagnostic techniques are of vital importance for the understanding, control and optimisation of
plasma processes [195]. The working principles are varied (optic, electric or magnetic) and the
information they obtain is often complementary, so that it is interesting to use more than one technique
at the same time. The local disruption produced by the probes is critical and, although the devices and
working principles are sometimes quite simple, the analysis of the signal usually raises difficulties [196].
The plasma parameters of significance to PSE processes can be summarised as follows [197]:
Electron density and electron energy distribution (electron temperature)
Type, density and energy of active species, i.e. ions, excited atoms and/or molecules.
Electromagnetic fields, which define the movement, spatial distribution, and time response of
the charged particles within the plasma.
Plasma diagnostic techniques have long been used to further understand the physics of plasma [198,
199]. In addition, once the underlying principles are known, they can also be used to provide real time
information about the process, and to feed control systems [171, 200, 201]. Optical emission
spectroscopy (OES) together with electric probes or collectors, are possibly the most extended plasma

diagnostic techniques. These methods are of importance to the present project and their basics will be
briefly introduced in the next sections.
3.4.1. Optical emission spectroscopy
As it was stated in a previous section, inelastic collisions take place within the plasma, mainly through
direct electron impact, producing ionisation and excitation of the gas atoms and molecules [194]:
−
efast + M → M + + eslow
− −
+ eslow (2.3-3)
− −
efast + M → M * +eslow (2.3-4)
where M is an atom or molecule and the superscripts + and * indicate the ionised and excited conditions
respectively, e stands for electron and the subscripts slow and fast indicate the energy of the particle. It
is evident that both M+ and M* are at higher energy levels than the atom or molecule at its ground state,
i.e. its normal equilibrium condition. The energetic species M+ and M* have relatively short lifetimes and
they experience decay processes, which frequently involve the emission of a photon to release the
surplus energy [202]:
M * → M + hυ (2.3-5)
where hν is the energy of the emitted photon, being h the Planck constant and v the frequency of the
photon. It is known from the atomic theory that the electron configuration and electronic energy levels
are quantised, i.e. they do not assume any value, but certain allowed energy states [203].
Consequently, if the atomic and molecular energy states are quantised, the energy involved in their
transitions must also be quantised; and this is the case of spontaneous emission, so that the energy of
the photon hv is quantised [131]:

ΔE = E k − E i = hv (2.3-6)
where Ek is the energy level associated with the energetic states M* or M+, and Ei is the energy level at
the ground state M, whilst hv is the energy of the emitted photon.
In this way, each decay transition emits a photon with certain energy, i.e. at one particular frequency,
giving rise to an emission pattern or spectrum, which can be used to identify the emitting species.
Moreover, the intensity of every emission line is proportional to the number of molecules at each energy
level, and the emission intensity has been used to correlate changes in the dominant ground state with
a treatment parameter [197]. However, quantitative information and absolute concentrations are difficult
or impossible to infer by this method.
The emission lines observed in atomic spectroscopy are due to the electronic transitions, i.e. changes in
the electronic configuration of the excited atoms. In addition to this, polyatomic molecules show a more
complex and finer structure, with different vibrational and rotational energy levels as a result of the
relative movement of the atomic nuclei in the molecule [202]. Although interactions between electronic,
vibrational and rotational energy levels exist, the energy difference is so large that, according to the
Born-Oppenheimer approximation, each level can be considered separately and superimposed to the
others, as shown in figure 2.3.4-1 and represented by the following equation [204]:
ΔE = ΔE E + ΔEV + ΔE R (2.3-7)
where EE, EV and ER are the electronic, vibrational and rotational energy levels respectively.

The emission lines are not sharp but diffuse, and usually called bands. The uncertainty principle
proposed by Heisenberg indicates that each transition involves a slightly different energy, thus emitting
photons at slightly different frequencies, which account for a natural line broadening [202]. The natural
line width is insignificant compared to the effect of Lorentz and Doppler broadening. The former is a
consequence of the collision of emitting species with other particles and the latter is associated with the
motion of the species while emitting light [131]. Moreover, the experimental broadening of the
equipment used to collect and analyse the light is often dominant.
The kit for spectroscopic observations typically includes an input optic device (telescope, collimator, or
optical fibres), which gathers light (figure 2.3.4-2). Optical fibres are frequently used to feed the light into
a monochromator, a polychromator or any similar equipment [205], where entrance slits or apertures
define the throughput and bandpass of the system [206]. The light is thus focused onto a wavelength
dispersing element, such as a grating or a prism, and a narrow range of wavelengths is reflected onto a
detector, such as a silicon photodiode or a PMT [207]. The collected spectrum shows the intensity of the
signal as a function of the wavelength, wavenumber or any equivalent scale.
OES is a popular diagnostic technique due to its simplicity, and also because it causes no disruption to
the plasma. It provides useful information on the type and, to some extent, the population of active
species in the plasma. High temperature optical fibres yield good spatial resolution, and have been used
in optical pyrometers to collect light from specific areas of interest [208, 209]. Although valuable, the
information obtained with OES is rather incomplete, and electric probes are necessary to obtain
evidence on the energy and density of electrons [197]. This will be discussed in the next section.

3.4.2. Electric probes
In order to understand the information obtained from electric probe devices, it is useful to make some
brief comments on the electric potential and mobility of charged particles in the plasma. It must be said
that negative ions and double ionisation events are very scarce in the type of plasma of interest to this
project, so that only electrons will be considered as negative charge carriers, and singly ionised atoms
and/or molecules as positive charge carriers [191]. Moreover, the probability of electron-ion
recombination in the volume (equation 2.3-8), i.e. the reverse of electron impact ionisation (equation
2.3-3), is rendered low by the necessary energy and momentum exchange among three particles [194]:
−
eslow −
+ eslow + M + → M + efast
−
(2.3-8)
where M stands for atom or molecule and e for electron, while the fast and slow subscript indicates the
energy or temperature of the particle. Volume recombination events are particularly unusual in gases at
low pressure, thus most of the recombination processes occur at the wall of the vessel that confines the
plasma, the latter acting as a third body.
As it was mentioned in a previous section, the potential between the electrodes is not evenly distributed,
but it is related with the density of charged particles, according to Poisson’s equation [210]:
d 2φ 4πe
= (ne − ni ) (2.3-9)
dx 2 ε0
where Φ is the potential function, x is the distance from the cathode, e is the elementary charge, ne and
ni are the density of electrons and ions respectively and ε0 is the permittivity of the free space. In the

field free space within the plasma, where quasi-neutrality is maintained, the onset of a space charge by
accumulation of ions is rapidly compensated and levelled by the highly mobile thermal electrons [191].
The accumulation of charges in the area surrounding the electrodes, the walls or any other foreign body
immersed in the plasma, produces a shield that confines the perturbation to a distance λD, according to
the Debye’s equation [194]:
ε 0 k BTe
λD ≈ (2.3-10)
ni e 2
where λD is the distance of the perturbation or Debye length, ε0 is the permittivity of the free space, kB is
the Boltzmann constant, Te is the electron temperature, ni is the ion density and e is the elementary
charge.
The flow of ions and electrons is governed by diffusion and by the electric field drift, according to the
following equation [194]:
∂n
Γ = −D + nμE (2.3-11)
∂x
Where Γ is the flux of charges, D is the diffusion coefficient, n is the density of charges, x is the distance
from the cathode, μ is the mobility of the charged particles and E is the electric field.
The flux of positive and negative charges out of the system must remain balanced in order to maintain
its electric neutrality. Moreover, if an insulated electrode is immersed in the plasma, the same amount of
positive and negative charges should arrive at its surface, so that no net flow of charges takes place
[211]. However, as the electrons are highly mobile compared to the ions, the flux of electrons to any
neutral surface exposed to the plasma would be larger than the flux of ions. Consequently, any foreign

body immersed in the plasma must develop a shield of negative potential in order to repel some of the
electrons, and thus balance the flow of negative and positive charges. This potential is called floating
potential, and depends on the type of gas, the pressure, and the electric discharge parameters.
Electric or electrostatic probes, frequently called Langmuir probes or collectors, are electrodes of known
area and defined shape (figure 2.3.4-3), usually made of tungsten, molybdenum or graphite, and
supported by an insulating ceramic or glass holder [196, 198]. The probes are immersed in the plasma
and electrically biased, sweeping a range of electric potential with respect to the plasma [212]. The I - U
curve is recorded and, providing the experimental settings and conditions are carefully selected and the
correct model is used to evaluate the signal, it gives valuable information on the characteristic energy
and density of electrons and ions [213].
Figure 2.3.4-4 shows the typical curve of a Langmuir probe. When the electrode is negatively biased,
the electrons are repelled and only ions are allowed to arrive at the surface of the probe [211]. If the
negative charge is not excessive, the ion flux is independent of the applied voltage, and it can be
measured from this part of the curve, called ion saturation region. On the contrary, when the probe is
positively biased, only electrons are allowed to reach the surface of the probe, thus the electron density
can be calculated. This part of the curve is called electron saturation region [196]. Between these two
extreme cases, the net flow of charge combines both electrons and ions, and the transition points give
information on the electron and ion temperatures, Te and Ti.
To this end, an improved version of the planar Langmuir probe or collector was designed to reduce the
effect of deposition or pollution on the effective area of the electrode [214, 215]. The working principle is
illustrated in figure 2.3.4-5. A capacitor is connected in series with the probe, and it is negatively biased,

or self-biased in case a radio frequency power supply is used [215-217]. The excitation or bias is then
interrupted and the capacitor is left to discharge by the arrival of positive charges from the plasma, i.e.
ions. The drain curve of the capacitor is recorded and gives very similar information to the ion saturation
region of a conventional Langmuir probe, according to the following equation:
dV
C⋅ = [Γi − Γe ] ⋅ eA (2.3-12)
dt
where C is the capacity connected to the probe, V is the potential across the capacitor, t is the time, Γi
and Γe are the flux of ions and electrons respectively, e is the elementary charge and A the effective
area of the probe.
This method is simple, and yields information with minimum signal post-processing. However, care
should be exercised to avoid edge effects on the probe, and to apply the right level of bias to produce
ion saturation, but not to disrupt the plasma conditions.

CHAPTER 3: EXPERIMENTAL PROCEDURES
1. Sample preparation
1.1. AISI 316 coupon samples
Coupon samples were cut from AISI 316 hot rolled bars (composition shown in table 3.1-1), using a high
precision Struers Accutom-5 cutting machine, fitted with SiC cutting discs. The final dimensions of the
samples were 25.4 mm in diameter and 6 mm in thickness. Both faces of the samples were wet ground
with SiC grinding paper of grit #120 until flat, and one face was ground further up to grit #1200. Samples
were then washed with soapy water and cotton, degreased with acetone in an ultrasonic bath for 10
minutes and dried with hot air.
Some samples were mirror polished with diamond pastes (6 μm and 1 μm) and colloidal silica
suspension, on a Struers DAP-7 automatic polisher. The cleaning procedure after polishing was
identical to the one described before.
Cross sections were cut from the samples with SiC cutting discs on a Struers Accutom-5 cutting
machine, nickel plated when necessary, and mounted on conductive bakelite using MetPrep PA30 or
Opal 400 mounting presses. The grinding, polishing and cleaning procedures were equivalent to the
ones described before.
Whenever it was required, the microstructure was developed by means of an etching solution of
composition 25 ml H2O, 25 ml HNO3 and 50 ml HCl. The sample of interest was immersed in the
solution at room temperature for a few tens of seconds, and immediately rinsed with water and dried
with hot air.
Chapter 3: Experimental procedures Page 57

Small AISI 316 coupon samples, 2 mm in thickness and 10 mm in diameter were prepared for EBSD
studies. The sample preparation procedure was equivalent to the one described before, with a careful
final polishing with colloidal silica to obtain a smooth and stress-free surface.
1.2. Friction force samples
These samples were cut from an AISI 316 bar, 4½ inches (114.3 mm) in diameter, using an automatic
cutting saw. Both faces were finely machined until flat and one face was wet ground with SiC grinding
paper up to grit #1200. The final dimensions of the samples were: 114 mm in diameter and 12 mm in
thickness, with a 16 mm through hole at its centre for holding purposes. The cleaning procedure after
grinding was equivalent to the one described before.
1.3. Corrosion samples
Samples were produced from an AISI 316 bar, 10 mm in diameter, for immersion corrosion
experiments. Rods 50 mm long were cut and an effective area 40 mm long and 8 mm in diameter was
finely machined and dry ground with SiC emery paper up to grit #1200. A flange at one end of the rod
(10 mm long and 10 mm in diameter) remained as rolled and was used for holding purposes (figure
3.1.3-1). These samples were subjected to the standard cleaning and degreasing procedures already
explained.
1.4. Transmission Electron Microscopy (TEM) samples
Coupon samples were cut and back thinned with SiC grinding paper until less than 200 μm thick,
leaving the treated surface untouched. Discs 3 mm in diameter were punched and further back thinned
with emery paper, until they were between 50 μm and 80 μm in thickness. Dimpling was conducted from
the back side of the sample in a South Bay Technology 515CE precision dimpling machine, using a

brass tool and 6 μm diamond paste with a 25 g load at a rotation speed of 140 rpm (14.66 s-1), reaching
a final thickness in the order of 10 μm to 20 μm.
Finally, the samples were mounted on copper discs, using a hot melt adhesive, and ion milled in a
Gatan 691 Precision Ion Polishing System (PIPS) until perforation occurred. The two Ar guns were set
at angles between 8º and 10º to ion mill the sample from a single side, i.e. the side opposite to the
surface treated layer. The ion current was between 8 μA and 14 μA at 4 keV, and the sample was
constantly rotated. Under these conditions, perforation happened within 2 hours. Samples were then
removed from the holder and the remaining hot melt adhesive was cleaned using acetone.
Some powder samples and wear debris were also prepared for TEM observation. The sample
preparation was, in these cases, very simple and consisted only in adding methanol to the glass
container where the samples were kept. A pipette was then used to select particles of suitable size,
which were deposited on a copper grid holder, 3 mm in diameter.
1.5. Residual Stresses (RS) bending thin disc samples
Thin discs, 25.4 mm in diameter and 0.5 mm in thickness, were cut from AISI 316 bars under carefully
controlled conditions, in order to obtain flat and parallel surfaces. Both sides of the discs were wet
ground with SiC paper, on a flat glass surface, up to grit #1200, and vibration polished with 6 μm
diamond paste for several hours (approximately 12 hours), until no traces of the grinding marks could be
observed. The previously described cleaning and degreasing procedures were applied and care was
taken to avoid stresses that could bend the discs. Finally, the discs were identified and their thickness,
roughness and flatness (in different directions) were measured in order to select the most suitable ones
for the assessment of the residual stresses developed during the surface engineering treatment.

1.6. Other samples:
The sample preparation methods here explained cover most of the types of samples of significance to
this project. Some other kinds of samples of different materials were eventually used: pure iron stripes,
AISI 304 stripes, glass slides, copper coupons, just to mention some. The sample preparation
procedures used in all these cases were very similar to the ones previously explained, and the
particularities of each case will be explained when necessary.
2. Surface engineering plasma treatments: experimental procedures
Three different plasma furnaces were used for surface engineering treatments (figure 3.2.1-1):
DC Klöckner Ionon 40 kVA unit for plasma carburising in DC and AS experimental arrangements
DC Klöckner Ionon 60 kVA unit for plasma nitriding in DC and AS experimental arrangements
AS Plasma Metal 75 kVA + 15 kVA industrial scale unit for AS plasma nitriding and carburising
The instrumentation was different for each furnace although, in general, it included mass flow meters to
control the gas mixture and gas flow, two pressure gauges of different kinds (Penning, Pirani or
Bourdon) to measure gas pressure, two K-type thermocouples protected by ceramic sheaths, and a
pyrometer for verification (KIU-PM350).
With regard to the procedure for plasma treatments, it could be generally described as follows:
The samples to be treated were cleaned and placed on the work table inside the furnace. In some
cases, a special holder or rig was required to keep the samples in position, for mechanical masking or to
produce the desired arrangement inside the chamber. Once the samples were in place, a vacuum
cleaner was used to remove dust particles that could have been deposited on the surface.

The chamber was then lowered and the ventilation valve closed. The cooling water began to circulate
and the vacuum pump was turned on to evacuate the furnace, up to a vacuum level in the order of 1 Pa.
Pure hydrogen gas was then fed into the chamber, and the main power supply was turned on to start
the plasma.
During the initial stage, the electric power (current and voltage) and the gas pressure in the chamber
were increased in steps, as a function of the temperature and the stability of the treatment (onset of
arcing), and the limit of the heating stage was usually set at 300ºC. From this point onwards, the gas fed
into the furnace was not pure H2 any more, but the gas mixture selected for the treatment, i.e. N2-H2 for
nitriding and CH4-H2 for carburising, or CH4-H2-N2 for nitrogen enhanced carburising. All the remaining
treatment conditions were automatically adjusted until the set point values could be reached
(temperature, pressure, gas composition and bias†) and these set point values were kept stable
throughout the duration of the treatment.
Once the treatment had finished, the feeding gas valve was closed and the chamber was evacuated.
The samples were left to cool down, under the residual treatment gas pressure, until below 80ºC. The
furnace was then ventilated and opened to remove the samples from the chamber. It was a normal
practice to clean the samples with soapy water and cotton immediately after the treatment, and this will
be considered the case unless otherwise mentioned.
The principal variables studied here were pressure and bias, although some other treatment conditions
were also assessed, with regard to gas composition (N2 enhanced carburising), treatment time and also
active screen treatments with different arrangements (figures 3.2.1-2 and 3.2.1-3). The process
†
Bias, as a set point, only applies to the active screen furnace and not to DC furnaces.

temperature, although of paramount importance for the diffusion treatment, has been already thoroughly
studied, and it has been found to be limited by metallurgical aspects of the AISI 316 alloy, namely the
formation conditions of expanded austenite and precipitation of secondary phases.
Therefore it was the objective of this study to optimise the plasma treatment conditions for a given
treatment temperature in order to produce a thick and uniform expanded austenite layer on AISI 316
samples free from surface defects, such as edge effects and arcing damage; and to increase the
understanding of the mechanisms of active screen treatments, and the main variables involved in the
process (tables 3.2-1 to 3.2-4 and figure 3.2.1-4).
3. Characterisation techniques
3.1. Hardness
Low force hardness and micro hardness tests were conducted in a Mitutoyo MVK-H1 durometer fitted
with Vickers or Knoop indenters. The load range was 10 g – 1000 g and calibration block #EP9716400
(757.3 HMV0.3) was used to check the condition of the equipment before each measurement. The
reported values are the average of at least six significative measurements and standards BS EN ISO
6507-1, 6507-2, 4516 and 4970 were taken as reference for these tests.
A Micro Materials nanotest system was used to conduct instrumented hardness tests and assess the
mechanical properties of the outmost layer of treated samples (BS EN ISO 14577-1 and 14577-4). Eight
indentations were conducted in each case under the testing conditions shown in table 3.3-1.

3.2. Roughness
Roughness measurements were conducted in a KozakaLab Surfcorder SE1700 stylus profilometer.
Standards BS EN ISO 4287 and 1134-1 were taken as reference for these measurements. Different
pick up settings were selected depending on the objective of the measurement (table 3.3-2).
3.3. Atomic Force Microscopy (AFM)
Contact mode atomic force microscopy was conducted in a Digital Instruments Dimension 3100
nanoscope, using Veeco NanoScope V.5.12r3 software and Veeco NP gold coated silicon nitride
probes (table 3.3-3).
3.4. X-Ray Diffraction (XRD)
A Philips X’Pert diffractometer was used to obtain the X-ray diffraction patterns (table 3.3-4). The
identification of the diffraction peaks was achieved by comparison with an XRD pattern database
PANalytical X’Pert HighScore 1.0d.
3.5. Glow Discharge Optical Emission Spectroscopy (GDOES)
A Leco GDS-750 unit was used to obtain the composition-depth profiles of plasma surface treated
samples. The method and measurement programme were calibrated using standard blocks of known
composition, according to the instructions of the manufacturer.
3.6. Optical Microscopy (OM)
Optical metallographic observations were conducted in a Leica Leitz DMRX microscope equipped with a
CCD camera for digital image acquisition.

3.7. Scanning Electron Microscopy (SEM)
Different scanning electron microscopes were used throughout the project, and for different purposes,
depending on their strengths and availability:
Philips XL30 – LaB6 filament (SEI, BSE, EDX)
Jeol 6300 – W filament (SEI, BSE)
Jeol 6060 – W filament (SEI, BSE, EDX)
Jeol 7000 – Field Emission Gun (SEI, BSE, EDX, EBSD)
3.8. Energy Dispersive X-Ray Spectroscopy (EDX)
Oxford Instruments Inca EDX detectors were used in all cases, controlled by means of Inca Energy
software. The internal calibration standards were considered valid for the purpose of this project and
only Ni or Co standards were used to correct the position of those reference peaks. The microscope
settings were optimised for the analysis (acceleration voltage, spot size, working distance, etc.)
3.9. Electron Back Scattered Diffraction (EBSD)
Crystallographic orientation maps (COMs) were obtained on a Jeol 7000 FEG SEM fitted with an Oxford
Instruments Inca Crystal Mk1 EBSD camera, at the general conditions listed in table 3.3-5. All the data
were collected and analysed using Oxford Instruments Inca Crystal software for EBSD.
3.10. Transmission Electron Microscopy (TEM)
Two transmission electron microscopes were used in this project:
Philips CM20 - LaB6 filament
FEI Tecnai F20 – FEG (EDX)

The micrographs and electron diffraction patterns (EDP) were obtained on Kodak SO-163 electron
image film (3 ¼ in x 4 in), developed and digitalised with 300 dpi resolution.
4. Tribological properties: experimental procedures
4.1. Wear tests
A custom-made pin-on-disc wear testing apparatus was used to assess the wear resistance of treated
and untreated samples (figure 3.4-1), and standard ASTM G99-05 was taken as a reference. Coupon
samples, 25.4 mm in diameter and 6 mm in thickness with a surface finishing of SiC paper grit #1200,
were rotated on a horizontal plane and worn against a steady WC-Co binder ball, 8 mm in diameter
(table 3.4-1). The tests were conducted under dry conditions in laboratory air at room temperature; the
relative humidity and room temperature were recorded for each test. The tests were 4.5 hours long, the
applied load was 10 N (Hertzian contact stress 1.6 GPa) and the sliding speed 0.031 m/s, giving a total
number of cycles of 17550 (for the coupon) or a sliding distance of 500 m (for the pin).
The matching surfaces were degreased with acetone, mounted on their respective holders and wiped
again with a clean cloth with acetone, to remove any contaminants from their surfaces. The tribological
couple was gently put into contact, and the load was applied 1 minute before sliding began. After the
test, the samples were carefully removed from their respective holders and observed. The wear debris
was collected for inspection and tested with a magnet. The profile of the wear track left on the tested
samples was measured at not less than 6 different positions, by means of a KozakaLab Surfcorder
SE1700 stylus profilometer (table 3.3-2). The obtained profile was integrated for the whole wear track
and the total worn volume could be thus calculated.

4.2. Friction tests
The friction tests were conducted on a pin-on-disc custom-made machine, equipped with a 100 lb
(45.36 kg) load cell and digital data acquisition card. Standard ASTM G115-04 was considered as a
reference in this case. The AISI 316 discs, 114 mm in diameter and a surface finishing of SiC paper grit
#1200, were mounted and rotated on a horizontal plane against a stationary 8 mm ball made of WC-Co,
AISI 316 untreated or AISI 316 plasma carburised. Tests were conducted under dry conditions in
laboratory air at room temperature, applying a load of 10 N and a sliding speed of 0.05 m/s. Several
tests were conducted on each disc, so that the rotation speed was adjusted according to the diameter of
the wear track in order to keep the sliding speed constant.
The matching surfaces were degreased with acetone and gently put into contact. The data collection
started when the load was applied, 15 seconds before sliding began, and continued throughout the 10
minutes duration of the test, at a frequency of 1 data point per second. After the test, the samples were
separated, removed from their holders and inspected. The wear debris was also collected and tested
with a magnet.
5. Corrosion behaviour: experimental procedures
5.1. Corrosion tests in boiling acid solution
Immersion corrosion tests in different boiling acid solutions were conducted to assess the corrosion
resistance of treated and untreated AISI 316 samples. The equipment consisted of a hot plate as heat
source, a 1 litre volume cylindrical flask where the boiling acid and the samples were kept, a flask lid
connected to a water coil condenser, and a vapour trap (figure 3.5-1).

To reveal the corrosion resistance of the tested samples under different conditions, various aqueous
solutions were used following British Standards BS EN ISO 3651-1 and BS EN ISO 3651-2:
16% mass fraction H2SO4
16% mass fraction H2SO4 with 100 g/l CuSO4 (BS 3651-2 Method A)
40% mass fraction H2SO4 with 25 g/l Fe2(SO4)3 5H2O (BS 3651-2 Method C)
20% mass fraction HNO3
The exposure times to the boiling acid varied from one hour up to 240 hours, the latter conducted in five
periods of 48 hours each.
The samples to be tested were ultrasonically cleaned in acetone and weighed. The coupon samples
were placed on glass Petri dishes to hold them and keep them separated from one another, and they
were immersed in the acid solution at room temperature. The specimens were placed on top of copper
coupons when copper contact was required (BS 3651-2 Method A). In the case of the rod cylindrical
samples, an especial holder was designed and manufactured to hang the samples leaving only their
effective area in contact with the acid.
Once the samples were placed in the flask, the solution was stirred with a magnetic follower, and heated
up to its boiling point (record was kept of the heating time), and kept boiling for the entire testing time.
Once the test had finished, the heat source was disconnected and the samples were immediately
removed from the boiling solution, rinsed with water and ultrasonically cleaned with acetone. Mass loss
measurements were thus conducted in an Avery Berkel analytical balance, with 0.1 mg accuracy.

5.2. Corrosion tests in acid at room temperature
These tests were conducted only with a 16% mass fraction H2SO4 aqueous solution at room
temperature and only on coupon samples. The polished samples were masked with fast drying acrylic
lacquer before being immersed in the acid solution for 120 hours at room temperature. After the test, the
samples were removed from the acid, rinsed with water and cleaned with soapy water and acetone to
remove the lacquer.
6. Plasma diagnostics – experimental procedures
6.1. Optical Emission Spectroscopy (OES)
OES spectra were first collected from outside the furnace, through a sight port window, using an
Optronic Lab OL730Q telescope (table 3.6-1). The telescope was placed 80 cm away from the window
and focused on the mesh of the active screen furnace, which resulted in a minimum source diameter of
20 mm approximately (figure 3.6-1). A cylindrical cone was made with white photographic cardboard
panel, its internal surface being covered with an opaque black liner, and placed between the furnace
and the telescope to reduce the stray light from reflections or other light sources. The use of such a
cone also helped to align the telescope and to keep the measuring distance constant.
A 1000 µm core fibre optic cable fed the light into a Jobin Yvon Triax 180 spectrometer, with a 190 mm
focal length and f/3.9 entrance aperture ratio (table 3.6-2). The optical arrangement consisted of
entrance and exit slits, collimating and focusing mirrors, and a grating turret in a cross Czerny-Turner
configuration. The turret was provided with two diffraction gratings, 150 and 1200 groves per millimetre,
for collection of low and high resolution spectra respectively. The low resolution grating allowed a
wavelength range of 1000 nm, while the high resolution grating admitted a total range of 0 nm to 1400
nm in steps of 100 nm. It must be mentioned that no signal could be collected below 250 nm, due to

absorption by the input optics and the air. The 1200 gr/mm grating yielded a spectral dispersion of 3.53
nm/mm and a spectral resolution of 0.3 nm at 500 nm.
A Jobin Yvon Spectrum ONE CCD thermoelectrically cooled detector head was used to measure the
light intensity at different wavelengths. In all cases, sufficient time was given for the detector to reach
the operating temperature before data collection (1 hour approximately). The CCD chip had a sensor
array 1024 pixels wide and 256 pixels high, no binning was applied and a flush cycle was run before
data acquisition, to reduce the noise. Data collection was controlled by a Jobin Yvon CCD-3000 unit, 16
bit ADC limit and 166 kHz conversion speed (table 3.6-3). The controller unit was operated from a PC
using SpectraMax software for Windows.
The automated entrance and exit slits were kept at the same width for optimum throughput. The
selected slit width was generally 0.04 mm for the measurements conducted with the telescope, and 0.08
mm for the spectra acquired with the optical fibre probe (method described below). The weaker signal
obtained with the optical fibres was counterbalanced by the increased slit width, i.e. increased bandpass
and throughput, although this also had an impact on the spectral resolution.
The system was calibrated, before each set of measurements, using the mercury green emission peak
at 546.074 nm (NIST online database, Pearse and Gaydon reference book) from a commercial
fluorescent lamp. In all cases, the Optronic Lab telescope was used to collect light from the lamp, and a
calibration accuracy of ±0.005 nm was usually attained. The manufacturer’s recommendations were
followed to calibrate the spectrometer, and the conditions used are listed in table 3.6-4.

The positioning accuracy was found to be well within the ±0.3 nm pledged by the manufacturer, and the
instrument calibration was not severely affected for one set of measurements, on condition that the
grating turret was not rotated to change the dispersing element. Nonetheless, all the spectra were
collected in the direction of increasing wavelength to minimise errors associated with clearances in the
driving mechanism of rotation of the grating turret.
The collection of light from inside the furnace, or intrusive OES (IOES), was achieved by using high
temperature resistant SiO2 optical fibres, 100 / 110 µm core diameter, numerical aperture 0.22 and UV-
Visible wavelength range (figure 3.6-1). A feedthrough was designed and manufactured to allow one
single fibre to have one end inside the furnace and exposed to the plasma, and the other end plugged
into the same Triax 180 spectrometer described before, by means of standard SMA connector (see
appendix A for construction details).
These types of measurements were only conducted in the active screen unit and consisted of the
standard heating stage, until the treatment conditions were reached. Next, spectra were collected
sequentially under different treatment conditions, allowing sufficient time for the work table bias to reach
stable values before each spectrum was acquired. Finally, an emission intensity map was produced with
each set of measurements and each map was produced twice for verification purposes.
6.2. Ion Flux Probe (IFP)
A planar electric probe, similar to a planar Langmuir collector, was built to measure the characteristic
parameters of the plasma in both DC and AS furnaces (refer to appendix B for construction details).
Before each measurement, the active surfaces of the probe were polished with colloidal silica, cleaned
with soapy water, ultrasonically cleaned with acetone and dried with hot air. The probe was then

mounted inside the chamber and connected with the measuring circuit placed outside the chamber, by
means of a standard electrical feedthrough. All ceramic insulators were wet ground and washed before
each experiment to eliminate the layer of conductive material deposited on them. Finally, the insulation
and continuity were checked before each measurement.
A low noise Instek GPS-6010 DC power supply with variable output voltage (0 V to 60 V) was used to
bias the probe. A Pico 2202 digital oscilloscope and 250 MHz oscilloscope probe, with an impedance of
50 MΩ and a X10 attenuation power, were used to acquire the drain curve of the tantalum capacitors
connected in series with the probe (UMAX = 63 V, C = 4.7 μF). The oscilloscope was connected to the
USB port of a PC and the signal was monitored and stored in the hard drive of a PC using PicoScope
5.15.6 (32 bit) data collection software.
The experiments in the DC furnaces consisted of a standard heating stage until the selected treatment
conditions were reached, followed by the data collection (approximately 1 hour) and the final cooling
down cycle. Two measurements for each condition were conducted, including DC and AS
arrangements, with standard carburising (CH4-H2) and nitriding (N2-H2) atmospheres, keeping
temperature and pressure unchanged (figure 3.6-2).
The measurements conducted in the AS furnace consisted of the usual heating stage, followed by data
collection in each of the treatment conditions of interest. A set of measurements in all the range of
selected conditions demanded up to twelve hours, as it was necessary to wait for the furnace conditions
to stabilise before collecting data. The whole range of conditions was divided into two parts, so that the
insulating paper could be changed and the ceramic spacers cleaned. Several curves were collected for
each condition, and the whole range of conditions was assessed up to three times.

The method of measurement consisted of charging the capacitor using the DC power supply, and
subsequently connecting the capacitor to the probe with the active surface exposed to the plasma. The
electric charge stored in the capacitor was such that the probe was biased to a potential some tens of
volts more negative than its floating potential. This negative charge repelled electrons and, in some
conditions, was enough to produce the so called ion saturation curve.
Under this condition, all the electrons were repelled and only the positive ions were allowed to reach the
probe surface. Therefore, the drain curve of the capacitor provided information on the flow of positive
ions to the probe. Once the negative potential dropped to low enough values, the high energy electrons
managed to surmount the retarding potential and reached the surface of the probe. The arrival of both
positive and negative charges to the probe produced a change in the discharge rate of the capacitor.

CHAPTER 4: RESULTS
1. Processing
AISI 316 samples were plasma treated in conventional DC furnaces, and these samples were adopted
as bench markers for the treatments carried out in the active screen industrial scale unit. Different
treatment conditions were explored in this AS furnace, in both nitriding and carburising atmospheres. As
a first approach, it must be said that AS processes had to be conducted under different conditions from
their DC counterparts (mainly, lower gas pressures), in order to obtain equivalent results. Furthermore,
the working conditions used for ASPC and ASPN also differed, particularly with regard to the bias level
(figures 4.1-1 and 4.1-2).
In these graphs, the bias is expressed in power units (kVA) for simplicity although, as it will be shown
later, only by reporting both the electric potential and the current density can the conditions on the
worktable be unambiguously defined. For one given power set point, the gas mixture and gas pressure
determine, to a great extent, the combination of current density and electric potential on the worktable.
The following equations were found to fit the data points with reasonable accuracy:
p = C ⋅ P −k3 (4.1-1)
C = k 1e − k 2 i (4.1-2)
1 ⎛ p ⋅ P k3 ⎞
i=− ln⎜⎜ ⎟⎟ (4.1-3)
k2 ⎝ k1 ⎠
where i is the current in Amperes, p is the pressure in Pascals, P is the power applied on the work table
in kVA and k1, k2 and k3 are constants, for which values depend on the gas mixture (table 4.1-1).
Chapter 4: Results Page 73

A saturation limit is reached at low pressure and with high enough applied power, so that any further
increase in the bias set point will not alter the actual parameters of the electric discharge. Under these
conditions, the current density is self limited, and the electric potential is frequently very high (ca 900 V).
If the gas pressure is increased, larger current densities can be drawn, and these are associated with
lower electric potentials on the worktable. Furthermore, edge effects occur on samples treated above
some current density threshold, so that the applied bias should be kept below a certain limit in order to
retain the benefits of the AS method.
AS treatments conducted within the range of effective conditions, shown in figures 4.1-1 and 4.1-2, were
less susceptible to process instabilities, and produced samples with homogeneous surface appearance.
However, inadequate processing conditions also rendered AS treated samples inhomogeneous in
morphology and properties. Figure 4.1-3 illustrates the arcing, hollow cathode and edge effects
frequently observed on a DC worktable. At the same time, the damage these effects produce on treated
components is apparent from figure 4.1-4, which also shows the comparatively improved surface quality
obtained with AS.
Further studies within the range of effective treatment conditions revealed differences between the
samples, particularly with regard to layer thickness. Figure 4.1-5 shows the layer thickness, measured
from GDOES nitrogen or carbon composition profiles, as the size of the bubble superimposed on the
map of treatment conditions presented before. It is evident from this figure that the optimum treatment
conditions lay in the low pressure and moderate bias level for ASPC, and even lower pressure and bias
level for ASPN. The layer thickness measured in each case is presented in tables 4.1-2 and 4.1-3, as a
function of the pressure and the bias level set point.

Therefore, it is within this region of effective treatment conditions that most of the work on
characterisation, wear and corrosion properties was conducted. The ASPC condition for maximum layer
thickness was found at 125 Pa and 15% bias, while the parameters for minimum incidence of edge
effect were 30 Pa and 5% bias. Samples treated under these two conditions were studied in particular
and the results will be presented in the following sections.
However, it is timely to mention here that some differences in the mean residual stresses (RS) were
evident from the bending of the ASPC treated thin discs. Figure 4.1-6 shows the typical profile of the RS
discs, before and after treatment, collected with a stylus profilometer. The classic Stoney’s formula and
some modified formulas proposed by other authors were used to calculate the mean stress in the
treated layer. The results show that the compressive residual stresses increased with the bias level and
layer thickness (table 4.1-4). Although these results are by no means accurate, they are of use to reveal
differences between the treatment conditions and to understand the behaviour of the samples in other
tests.
2. Characterisation of plasma carburised AISI 316
AISI 316 samples plasma carburised in a DC furnace were adopted as bench markers for the
treatments carried out under active screen arrangements. All the plasma carburising processes were
conducted within the range of optimised conditions mentioned in the previous section. DC and AS
treated samples showed the typical features and properties reported for carbon expanded austenite, as
it will be shown in what follows.
Observation under the optical microscope revealed some changes in the microstructure after plasma
carburising. The treated samples showed clear grain contrast due to slip bands, which appeared at

different orientations depending on the activated slip systems (figure 4.2-1). The slip bands can be
clearly seen in the crystal orientation maps (COMs) obtained with EBSD on the same area of the
sample before and after plasma carburising (figure 4.2-2). The EBSD pattern quality deteriorates after
the plasma diffusion treatment, and this seems to be related with the high density of defects introduced
into the crystal structure. The density of defects increases progressively as the layer grows with
treatment time (figure 4.2-3)
The typical appearance of the treated layer can be seen from the cross section micrograph in figure 4.2-
4. It consists of a white featureless layer which, in contrast to the substrate, is not affected by the
etchant. This higher resistance to the etching agent can be considered as a first rough indication of
some degree of increase in the corrosion resistance of the treated material.
With regard to morphology, a significant difference between DCPC and ASPC could be observed under
SEM and AFM. Figure 4.2-5 shows the SEM high magnification micrographs, where some irregular
morphology is seen on the surface of a DCPC sample, compared to the uniform appearance of the
ASPC sample. This aspect was confirmed by AFM, as illustrated in figure 4.2-6, where the DCPC
sample exhibits an uneven surface morphology in contrast to its ASPC counterpart.
The TEM studies conducted on the outmost layer of treated specimens revealed a slightly thicker oxide
layer on the ASPC sample compared to the DCPC one (figure 4.2-7). A layer of particles was found to
cover all the surface, and the typical morphology is shown in figure 4.2-8, together with the ring electron
diffraction pattern (EDP) obtained on that same area. The particle size was between 25 nm and 30 nm
for DCPC and between 30 nm and 40 nm for ASPC, whilst the indexing matched some iron and

chromium carbides of composition Fe3C, Fe2C5 and Cr23C6 in both cases. Figure 4.2-9 shows the fcc
diffraction pattern corresponding to austenite, which was obtained from the underlying material.
The XRD peaks shown in figure 4.2-10 were obtained from DCPC and ASPC samples and correlate
with the austenite stick pattern in both cases. Only one additional diffraction peak of low intensity was
found at 39.55º, which could be attributed to Hägg Carbide of composition Fe5C2. The peaks are sharp
with a slightly asymmetric pseudo Voigt profile, and they exhibit order dependent widening compared to
the untreated material. However, the reflections are shifted to lower angles, and the shifting varies with
the 2θ angle. The analysis of this shifting and the calculated lattice parameters indicate that DCPC and
ASPC produce the same degree of carbon supersaturation and lattice expansion (figure 4.2-11).
Figure 4.2-12 shows the typical GDOES composition-depth profiles for carbon, corresponding to DCPC
and ASPC treated samples. As it is evident from this graph, there is a high degree of correlation
between both curves in what concerns to the degree of carbon supersaturation, the composition profile,
and also the layer thickness. A drop in carbon content is seen within the first 1 μm of the ASPC sample,
which was found to match a small nitrogen peak. The active screen industrial scale unit was used for
both plasma nitriding and plasma carburising, and it was not possible to remove all traces of nitrogen,
even after several hours of consecutive carburising treatments.
With regard to hardness, figure 4.2-13 shows the Vickers microhardness values obtained on DCPC and
ASPC samples using different loads, which serve as an indication of the load bearing capacity (LBC) of
the treated layer. Once again there is a significant degree of correlation between both techniques. The
ASPC samples showed some higher values at low indentation loads (25 g) which can be explained by

the nitrogen content of this outmost layer, and the slightly higher carbon content. On the other hand, the
hardness of ASPC at 100 g indentation load was marginally lower than their DCPC counterparts.
The hardness values obtained with higher loads were virtually the same. However, some cracks were
found inside and around the indentations conducted on DCPC specimens (figure 4.2-14). These cracks
appeared at indentation loads higher than 500 g and are not considered as a failure of the treated layer,
although they are an indication of a slight reduction in ductility.
The instrumented hardness tests conducted on AISI 316 untreated and plasma carburised samples
confirmed a considerable increase in hardness and a small rise in the elastic modulus of the material
after the plasma diffusion treatment. The curves in figure 4.2-15 illustrate the applied load against the
displacement of the indentor, and the main results are summarised in table 4.2-1.
3. Study of the mechanisms of active screen plasma surface engineering
The set of experiments described in table 3.2-4 was conducted in order to understand the mechanisms
involved in ASPC and the differences between the ASPC and the ASPN treatments. For the purpose of
this assessment, ASPN was considered the yardstick for ASPC, as the former has been studied and
discussed in further detail than the latter.
In first place, it must be said that the samples subjected to floating potential (i.e. arrangement C in figure
3.2.1-2) showed no hardening effect, and no signs of diffusion of carbon or nitrogen could be identified.
Even though this evidence is of significance for the understanding of the mechanisms involved in active
screen treatments, no further details will be given, since all the characterisation was identical to the
untreated AISI 316 substrate.

On the other hand, DC and AS treated samples showed some hardening effect, although the results
were dissimilar (arrangements A and B in figure 3.2.1-2). As the first approach, all DC treated samples,
i.e. DCPN, DCPC and DCPCN, showed the characteristic edge effect; the ASPN and ASPCN samples
had a very uniform surface appearance, whilst the ASPC sample exhibited a patchy morphology, which
resembled the shape of the mesh used as active screen in this experiment (figure 4.3-1).
The XRD peaks shown in figure 4.3-2, for AISI 316 samples treated under different conditions, indicate
that austenite is the only phase in all cases. However, the characteristic shifting and widening of the
diffraction peaks of expanded austenite vary for each case. The shifting and widening is clearly seen
after nitriding treatments (both DCPN and ASPN), whereas these effects are weaker on DCPC and
DCPCN specimens, and almost no shifting or widening can be seen on ASPC and ASPCN samples.
The GDOES composition-depth profiles, obtained from this same set of samples, indicate the typical
results after DC treatments: nitriding, carburising and N2 enhanced carburising (figure 4.3-3). On the
other hand, a significantly different response is once again evident after AS treatments. ASPN shows a
similar nitrogen profile to DCPN, although the penetration depth was shallower; a similar result is
observed for ASPCN, but the treated layer was significantly thinner in this case; finally the composition
profile obtained from ASPC samples evidences very shallow carbon diffusion.
The LBC, assessed by means of Vickers microhardness at different indentation loads, confirmed the
GDOES data (figure 4.3-4). The hardness values obtained for the nitrided test pieces were very high at
low loads, and decreased rapidly at higher loads, with the onset of cracks around the indents (figure 4.3-
5). On the other hand, the DCPC samples gave lower hardness values, with a gradual reduction, typical
of the carbon diffusion profile; whilst its ASPC counterpart indicated little hardening effect. A similar

trend was observed on the DCPCN and ASPCN specimens, although the hardness results obtained on
DCPCN show a plateau region, which also fits the GDOES composition profile.
As part of this set of experiments, AISI 304 stripes were treated in AS arrangements using a mesh with
large holes, 25.4 mm in diameter. The hardness measurements conducted on these test pieces are
shown in figure 4.3-6, and indicate an apparent difference between the areas uncovered (holes) and the
areas covered by the cage in the case of nitriding. On the contrary, no differences are seen for
carburising and N2 enhanced carburising, in which virtually no hardening took place.
The roughness measurements performed on treated coupons showed some differences, as it can be
seen from table 4.3-1, with DC treated samples showing consistently higher roughness values than their
AS equals. A closer observation of AS treated specimens put into evidence the existence of a layer of
deposited material on them. This was obvious on the copper coupons, some of which exhibited a silver
colour after the treatment (figure 4.3-7).
SEM and AFM detailed studies showed a morphology analogous to the one described in the previous
section, with particles of different sizes depending on the treatment conditions. In general, the ASPN
samples appeared to be covered by a layer of fine particles, 50 nm to 100 nm in diameter, while the
ASPC and ASPCN treated specimens showed a much coarser and irregular structure (figure 4.3-8).
The use of glass slides and copper substrates produced enough contrast with the deposition layer as to
allow for some degree of identification of the present phases with XRD. Figure 4.3-9 shows the data
collected from copper coupons and, in all cases, they show a perfect match with the peaks of the Cu
standard. However, two small additional peaks at 41.69º and 44.89º can be seen after AS treatments,
which could be attributed to FexN and (Fe, Cr)xCy respectively.

In the case of the glass slides, the deposition layer formed after ASPC and ASPCN was dusty, and did
not resist the cleaning procedure, whilst the deposition produced by ASPN was surprisingly coherent
and adherent (figure 4.3-10). The latter was analysed by means of XRD, and the diffraction peaks
matched several FexN compounds, and showed good agreement with the FeN pattern (figure 4.3-11).
This finding is of relevance for the understanding of the mechanisms of active screen plasma surface
engineering and will be discussed in the next chapter.
Finally, the mesh used for the experiments on the mechanisms of active screen plasma surface
engineering was observed under the SEM and analysed by EDX to confirm its composition. The results
proved that the mesh used for these experiments was AISI 304, and the typical micrograph and EDX
spectrum are shown in figure 4.3-12. A similar analysis was conducted on the mesh of the AS industrial
unit, and this was found to be made of low carbon steel (figure 4.3-13). In both cases, the deposited
material found on the samples exhibits some interesting correlation with the material of the mesh.
4. Tribological properties
The wear resistance of AISI 316 untreated (UT), DC plasma carburised (DCPC) and active screen
plasma carburised under two conditions (ASPC 125 Pa – 15% bias and ASPC 30 Pa – 5% bias) were
compared. The treatment conditions selected for this assessment followed the same rationale
mentioned in the section on processing, i.e. conditions of maximum layer thickness and minimum
incidence of edge effect, respectively. Table 4.4-1 summarises the obtained results.
The appearance of the coupon samples after the wear tests evidences the difference in the wear
response of the two materials (figure 4.4-1). The same is observed in the pictures of the counterpart
WC-Co balls, in figure 4.4-2. It is also worth mentioning that a significant amount of wear debris was

produced during the wear test of the untreated material, in contrast with the very small amount found
after the test in the case of all the treated samples. These three aspects of the wear tests will be
described in further detail in what follows.
The measured wear volume indicated a marked improvement of all treated samples over the untreated
AISI 316 substrate (figure 4.4-3). The worn volume of the expanded austenite was more than two orders
of magnitude lower than that of the untreated AISI 316. On the other hand, no significant difference
could be appreciated between the DCPC and the ASPC treated samples. All the treated samples
exhibited wear properties typical for carbon expanded austenite.
A closer observation of the wear tracks under SEM revealed differences in morphology. The untreated
AISI 316 suffered from abrasive and adhesive wear, while the treated samples developed a protective
oxide layer. The difference in morphology can be appreciated in figure 4.4-4, and the composition of the
oxide layer is evident from the EDX maps in figures 4.4-5 and 4.4-6. The layer is mainly formed by iron
and chromium oxide, but some tungsten is also present (table 4.4-2). The latter evidences the transfer
of material from the counterpart ball, and the formation of the so called third body during sliding. It is
also interesting to note that nickel does not seem to follow the same pattern as chromium and iron.
Regarding the counterpart material, the size and shape of the wear scars on the WC-Co balls matched
the width of the wear tracks left on coupon samples (figures 4.4-2 and 4.4-7). Detailed studies of the
morphology and composition, under the SEM, revealed accumulation of material at the trailing edge
(figure 4.4-8). This is more evident in the ball worn against the plasma carburised material. However,
the SEM pictures and the EDX composition maps (figures 4.4-9 and 4.4-10) indicate that the amount of

material transferred from the coupon sample onto the counterpart ball is larger in the case of the
untreated AISI 316. This is a clear evidence of severe adhesive wear of the untreated material.
The WC-Co balls worn against untreated AISI 316 showed a significant amount of iron and chromium
on the wear scar. The oxygen signal was also strong, as the tests were conducted in laboratory air, and
the high pressures and temperatures developed in the contact spots favoured oxidation (figure 4.4-9).
On the other hand, the WC-Co balls worn against expanded austenite only displayed minor traces of
iron oxide on the wear scar, and a small amount of material accumulated at the trailing edge (figure 4.4-
10). It is evident that less material is transferred from the coupon sample onto the counterpart ball in this
case.
With regard to the wear debris, obvious differences were found once again between the treated and the
untreated specimens. The latter produced a significant amount of black debris during the sliding wear,
and a simple test with a magnet revealed it responded to the magnetic field. Under the OM, the particles
were 20 μm to 30 μm in size and metallic shiny (figure 4.4-11). The wear tests conducted on plasma
carburised material produced small amounts of reddish-brown debris. This time, the particles were
mostly non-magnetic, and only a few responded weakly to the magnetic field. OM observations showed
the particles had a mean size of 10 μm with a plate-liked shape (figure 4.4-11).
The wear debris was observed under SEM and TEM in order to study their morphology and identify their
nature. In both cases, the debris was found to be a conglomerate of smaller particles, but the particles
were finer in the case of the plasma carburised material than in the untreated AISI 316 (figure 4.4-12).
The ring electron diffraction patterns indicated possible martensite and magnetite matches for the
untreated material (figure 4.4-13). This is in agreement with the appearance and magnetic properties

observed in the particles. On the other hand, the AISI 316 PC gave a possible haematite match, which
once again correlates with the previous observations. However, an oxide of mixed nature must be
present in this case, as the EDX spectrum exhibits the unequivocal presence of other alloying elements
(figure 4.4-14). Table 4.4-3 summarises the findings on wear debris.
XRD was used to identify the phases present in the wear track of AISI 316 specimens. The intensity of
the reflection shown in figure 4.4-15 is not considerable, but it fits the martensite pattern. In addition to
this, microhardness measurements conducted on the wear track gave an average hardness of 560
HMV0.01, which is significantly harder than the austenitic substrate. The hardness profile conducted on
the cross section of the wear track clearly shows the hardening effect and, possibly, martensitic phase
transformation (figure 4.4-16). Strain induced phase transformation is likely taking into account the
severe deformation observed in the subsurface of the untreated material (figure 4.4-17).
EBSD phase and crystal orientation mapping gave some further evidence on the extent of the
deformation and martensitic transformation. Figure 4.4-18 shows a similar SEM cross section image
(without etching), and the EBSD map for austenite and martensite. These images show a 15 μm thick
layer in which strain induced martensitic phase transformation took place, to some extent. Plastic
deformation is evident up to a depth of 60 μm, and some degree of work hardening is also assumed to
be associated with this phenomenon.
The study here presented indicates that work hardening took place during the wear tests of untreated
AISI 316 against WC-Co. Moreover, evidence of strain induced martensitic transformation was found by
means of TEM, XRD, EBSD and microhardness.

On the other hand, the same study conducted on the plasma carburised material yielded very different
results. The electron diffraction pattern obtained with TEM did not match the martensite pattern; the
XRD studies only showed reflections corresponding to austenite; and the microhardness profile
conducted on the cross section was identical to a normal plasma carburised specimen. Only the EBSD
orientation maps showed some evidence of deformation close to the surface (figure 4.4-19). However,
this deformation was attributed not only to the shear stress of the wear test, but also to the distortion
introduced by the carburising process itself.
The graphs in figure 4.4-20 show the friction signals obtained during sliding tests under similar
conditions to the wear tests reported before. The results are summarised in table 4.4-4.
The AISI 316 UT couple (UT vs UT) produced an average coefficient of friction of 0.6 with fluctuations,
in agreement with the literature. A large amount of wear debris was released during the tests, which was
metallic in appearance, and magnetic. The WC-Co ball (UT vs WC) yielded lower friction coefficients,
and left some stick-slip markings on the wear track and no significant debris; whilst the PC ball sliding
on AISI 316 (UT vs PC) showed an intermediate behaviour in all these aspects. In general, the
coefficient of friction clearly peaked when sliding started (μstatic), and subsequently decreased
asymptotically to its steady sliding value (μdynamic).
The friction signal for the AISI 316 untreated ball sliding against a PC disc (PC vs UT) exhibits
significant instabilities with very high friction peaks. The peaks in the friction force correlated with
intense noise during the test, and a considerable amount of black magnetic debris was produced. Both
the WC and the PC balls sliding on PC discs (WC vs PC and PC vs PC) yielded lower coefficients of
friction and produced small amounts of reddish brown wear debris, mainly non-magnetic (only some

particles responded to the magnet). The friction force displayed a relative maximum at the beginning of
these tests, followed by a period of low friction and a final increase up to the final steady friction
coefficient, which was higher than the initial relative maximum (μstatic < μdynamic).
5. Corrosion behaviour
The initial immersion corrosion tests conducted in a sulphuric acid solution (16% mass fraction) at room
temperature produced very little corrosion in all the test pieces. The AISI 316 samples were found to
change the appearance to a tarnished grey colour after only 10 minutes of exposure to the acid, while
the PC samples retained their metallic shine throughout the experiment. OM and SEM observations of
the corroded specimens revealed intense corrosion on MnS inclusions in the AISI 316 coupons, and
failure of the outmost deposited layer of carbides in their ASPC equals (figure 4.5-1). The test was
repeated with PC samples polished after treatment, on which no deposition layer remained, and no
significant features or morphology could be observed in this case.
The tests conducted at boiling temperature in the same sulphuric acid solution (16% mass fraction)
revealed clear differences between the specimens, as can be seen from figure 4.5-2. Corrosion was
catastrophic on AISI 316, while the layer of EA was left virtually intact. The edges of DCPC 400 and
ASPC 125 test pieces showed some contrast with the rest of the surface area, associated with some
degree of edge effect. On the other hand, the ASPC 030 sample showed a very uniform surface
appearance. The cross sections in figure 4.5-3 illustrate the different behaviour of the AISI 316 UT and
AISI 316 PC (EA).
Detailed observation under SEM revealed some localised corrosion on the EA layer. The attack was
particularly intense on MnS inclusions and, once the substrate was exposed, cavities of considerable

size were formed in the subsurface (figure 4.5-4). Some localised attack was also detected on slip
bands, even in the early stages of the tests, although corrosion progressed slowly and the layer was still
unbreached after 20 hours of exposure to this corrosive solution (figure 4.5-5). Finally, the grain
boundaries were found to be vulnerable to localised corrosion, and this type of attack was clearly
identified on samples exposed for 15 hours or longer periods of time (figure 4.5-6).
With regard to the preferential corrosion on slip bands and grain boundaries, it must be mentioned that
these were observed more frequently on DCPC 400 and ASPC 125 samples than in the ASPC 030
ones, which were actually free from intergranular corrosion. In all cases, corrosion was more intense
close to the edges of the samples, where the density of slip bands was higher and the grain boundaries
appeared to be weaker. Once the layer of EA was breached, preferential dissolution of the substrate
took place rapidly creating large subsurface pits, with some grain boundaries failing first (figure 4.5-7).
The tests performed on cylindrical specimens yielded similar results, with catastrophic corrosion of the
AISI 316 substrate and mild corrosion of the treated samples, which took place, mainly, through defects
in the EA layer (figure 4.5-8). The AISI 316 samples turned black after only a few minutes immersed in
the corrosive solution, and a considerable amount of gas bubbles formed on their surface, which was
attributed to the cathodic evolution of hydrogen. On the other hand, the PC samples retained their
metallic appearance, although they became dull after the test. The evolution of hydrogen was not so
profuse in these last cases.
The localised attack at the centre of the rods is noteworthy, and was attributed to the presence of MnS
stringers; while the extended damage towards the edges of specimen DCPC 400 was believed to be a
consequence of stronger edge effects produced by these treatment conditions. Finally, this tests also

provided quantitative data in the form of the average mass losses (3 samples per condition), which are
shown in figure 4.5-9. The mass losses of all PC specimens were between 4 and 6 times lower than
their untreated AISI 316 counterparts.
Corrosion tests conducted in H2SO4 16% solution with addition of CuSO4 while in contact with metallic
copper, produced very little corrosion of the AISI 316 substrate, though some degree of attack was
found on defects of the EA layer. In this solution, the evolution of hydrogen was replaced by the
cathodic reduction of copper ions, and no gas bubbles were seen to form on the surface of the test
pieces. As it can be seen in figure 4.5-10, the edges of the specimens were more susceptible to
localised corrosion, especially in the case of specimens DCPC 400 and ASPC 125, whereas their ASPC
030 and AISI 316 counterparts displayed very homogeneous appearances.
Closer observation with OM revealed preferential attack on slip bands in all the treated samples (figure
4.5-11). However, grains with higher density of slip bands were more severely attacked, so that
corrosion was more extensive on DCPC 400 specimens, followed by ASPC 125 and ASPC 030. With
regard to grain boundaries, even though no grains were dislodged and no severe intergranular corrosion
was observed, some ditch type grain boundaries were seen on coupons DCPC 400 and ASPC 125; the
edges of the samples were particularly vulnerable to this type of attack.
SEM and AFM studies of the corroded grain boundaries revealed they were the result of the
coalescence of pits at the intersection of the slip bands with those grain boundaries, to form a
continuous trench (figure 4.5-12). Moreover, EDX composition line scans provided some evidence of
carbon enrichment in the area surrounding the trench, although this is not conclusive as no correlation
could be found with carbide forming elements, particularly chromium (figure 4.5-13).

The gravimetric tests conducted on the test pieces corroded in boiling H2SO4 16% with CuSO4 indicate
very low mass losses, two orders of magnitude lower than the values reported for H2SO4 16% solution.
Even though the figures are not conclusive, the corrosion factors in table 4.5-1 show a trend that is
helpful to understand the results and rank the treatments according to their corrosion resistance.
Two other corrosive solutions were adopted in order to assess the susceptibility of the grain boundaries
of the PC samples to localised attack: sulphuric acid 40% solution with iron sulphate, and nitric acid
20% solution. The former test was conducted for 24 hours and produced a very similar attack to the one
observed with copper sulphate. Corrosion was more intense on defects in the EA layer, mainly slip
bands, and some pits coalesced to produce more severe localised attack and form some ditch grain
boundaries. The edge effect was revealed in the case of DCPC 400 and ASPC 125, while the ASPC
030 and AISI 316 exhibited a very even morphology.
In the case of nitric acid, the test was conducted for a total of 240 hours, in 5 periods of 48 hours in
which the solution was renewed. The appearance of these samples differed slightly from previous tests,
principally with regard to the attack on grain boundaries. As it can be seen from figure 4.5-14, the
untreated AISI 316 suffered some mild attack and only the grain boundaries were developed after the
test. On the other hand, all PC samples exhibited localised corrosion on slip bands and pits, which were
larger and more numerous on the DCPC 400 specimens, followed by the ASPC 125 and the ASPC 030.
No grains were dislodged during the test, but ditch type grain boundaries were clearly observed under
AFM, having a depth of, at least, 0.8 μm (figure 4.5-15). In these cases, the grain boundaries had the
appearance of a continuos trench surrounding full grains, and no traces of primitive pits could be
identified. Some severe localised corrosion was found in PC samples, which was attributed to the

presence of inclusions (figure 4.5-16). This type of attack was clearly present in all cases and, although
it was not generalised, the depth of the pits was enough to be taken into consideration as a failure mode
of the EA layer. In contrast, the corrosion rates calculated from gravimetric measurements indicate that
the corrosion rate of the PC samples becomes comparable to the one of AISI 316 untreated substrate,
after an initial period of high dissolution (figure 4.5-17).
6. Plasma diagnostics – Optical emission spectroscopy
The OES spectra collected with the telescope through the sight port of the furnaces were useful to
identify the most common active species involved in electric discharges through different gas mixtures,
i.e. CH4–H2, CH4–N2–H2 and N2–H2. The spectra in figures 4.6-1 to 4.6-3 show some of the differences.
The signals collected through the sight port for DC and AS experimental arrangements were virtually
identical, although the emission intensity was slightly higher in the AS setting, due to the hollow
cathodes formed on the mesh.
In the case of plasma carburising (CH4–H2), the spectrum was very scarce in peaks, and only the
atomic hydrogen Balmer series could be seen. The Hα at 656.125 nm dominated this wavelength range,
and only some weak H2 and CH+ peaks completed the spectrum. For the nitrogen enhanced plasma
carburising (CH4–N2–H2), the addition of only 1% N2 changed the shape of the spectra in a considerable
way, and the CN (violet system) and N2+ (first negative system) bands were clearly present, although
the Hα line remained to be the most intense. Finally, the spectra for plasma nitriding were dominated by
the N2+ (first negative system) bands which, under some conditions, were even more intense than the
Hα emission line. Some NH, hydrogen and nitrogen peaks completed the spectra.

The study of OES emission spectra under different active screen conditions was found difficult to
conduct with this experimental arrangement, i.e. from outside the furnace. When measurements were
done through the sight port, the telescope was focused on the active screen itself (the mesh), which is
designed to form hollow cathodes. These hollow cathodes changed their position, quantity and intensity
depending on the treatment conditions and, as a result, they also made the collected OES signal erratic.
In conclusion, no clear correlation could be observed between these emission spectra and the AS
treatment conditions.
The optical fibres used to probe the AS industrial unit yielded optical signal directly from the worktable,
which was found to vary consistently with the treatment conditions, although this was achieved at
expense of signal intensity and signal-to-noise ratio. Therefore, only the strongest emission lines and
bands could be used for this purpose, and the Hα and Hβ peaks of the Balmer series at 656.125 nm and
486.003 nm respectively, were selected in the case of plasma carburising‡, whilst the N2+ emission band
at 391.44 nm was chosen for the assessment of plasma nitriding. The emission intensity was recorded,
for each gas mixture, at different working pressures and bias levels, and the information was
consolidated in graphs of the kind shown in figure 4.6-4.
The OES maps thus obtained exhibit increasing intensity with increasing level of bias, and this intensity
is higher in the low pressure region. As it was mentioned in a previous section, low working pressures
imposed a limitation on the level of bias and, consequently, on the emission intensity. Increasing the gas
pressure allowed a further increase in the applied bias, and the emission intensity responded
accordingly. However, this was true only until some pressure threshold was reached, and the relative
maximum in emission intensity was found to agree with the conditions identified for maximum layer
‡ The use of the H emission lines was justified because atomic hydrogen is a by-product of the decomposition of the
methane molecule and trials showed some sensitivity of peaks in the Balmer series to the amount of CH4 in the gas mixture.
Nevertheless, the identification of clear and strong carbon containing species would of course be of interest.

thickness. Once the pressure threshold was exceeded, the emission intensity fell even for very high
levels of bias; this point was found at higher pressures for ASPC than for ASPN (figure 4.6-5).
The optical signal was plotted against different electric parameters and some trends were revealed,
depending on the gas pressure and the gas mixture (figure 4.6-6). The emission intensity plotted as a
function of the bias voltage showed some quadratic trend at high pressure, while the data points
obtained at low pressure deviated from this line. Both ASPC and ASPN exhibited very similar responses
to the electric potential of the worktable. The emission intensity was found to vary linearly with the
electric current, although the slope was affected by the gas pressure and, furthermore, a clear breaking
point was found in ASPN, whereas this was not visible for ASPC. Finally, the emission intensity showed
considerable correlation with the bias power applied on the work table, with slight changes in slope for
ASPC and a clear breaking point for ASPN.
7. Plasma diagnostics – Ion flux probe
The use of the IFP under AS arrangements inside a DC furnace indicated a strong electrostatic coupling
with the active screen electric input. This was concluded from the oscillations in the floating potential
(FP) of the electrostatic probe, which perfectly matched the electric input characteristics of each furnace
(figure 4.7-1); while the same experiments conducted in conventional DC arrangements showed only
background noise on the FP electric signal. Figure 4.7-2 shows the differences in FP between the DC
and AS arrangements, which was seen to depend on the gas mixture and gas pressure used for the
experiment. In addition, the flux of ions was measured and the obtained results indicate appreciably
higher values in the case of the AS setting, although it must be said that these figures bare considerable
error.

A similar type of analysis was conducted inside the AS industrial unit, and the oscillation in the FP of the
electrostatic probe was once again in agreement with the power input of the furnace (figure 4.7-3). The
average value of the FP was also found to vary with the treatment conditions, shifting to more negative
values with increasing bias and pressure (figure 4.7-4). However, a limitation imposed on the applied
bias was once again found at low gas pressure, and the FP values were observed to remain constant or
even decrease slightly once this bias saturation level was reached. Unfortunately, only a reduced range
of treatment conditions could be assessed because of limitations in the probe and the measuring circuit.
An attempt was made to calculate the ion flux from the drain curve of the capacitor of the IFP measuring
circuit. Figure 4.7-5 shows the drain curves obtained with the worktable under floating potential for
ASPC and ASPN at different gas pressures. The different responses were clear, and the capacitor was
drained several times faster in the low pressure range, indicating a higher rate of arrival of positive
charges onto the effective surface area of the probe. Some measurements were also conducted under
normal treatment conditions, although the range was seriously restricted by limitations of the probe and
the measuring circuit, and the errors make these figures unreliable. In general, it can be said that the
calculated ion fluxes increased with bias and decreased with gas pressure (figure 4.7-6).

CHAPTER 5: INTERPRETATION AND DISCUSSION
1. Active screen processing conditions
The current-voltage characteristic curves obtained in the AS furnace indicate a non-linear relationship
typical of abnormal glow discharges, with the current density increasing more rapidly at higher
pressures (figure 5.1-1) [190, 192]. The two constraints found in the operating conditions, namely the
onset of edge effects and the current saturation, are relatively well known phenomena.
The edge effect is a result of the local increase in the electric field, and the consequent higher ionisation
rate and higher current density [218]. This obviously declines when lower electric potentials are applied,
although it has also been reported that low pressure discharges are less sensitive to concentration of
electric field on sharp edges [219].
The current saturation can be attributed to a low density of charge carriers and to technical limitations of
the power supply. In the plasma, the density of electrons is approximately the same as the density of
ions (ne ≈ n+), and the current density can be expressed as [220]:
j = en e μ e E = σE (5.1-1)
where j is the current density, e is the elementary charge, ne is the electron density, μe is the electron
mobility, σ is the conductivity of the weakly ionised gas, and E is the electric field. The value of E is
defined by the potential delivered by the power supply (UMAX = 926 V for the AS furnace) and the
distance between the electrodes in the furnace, which impose the first limitation.
Chapter 5: Interpretation and discussion Page 94

The conductivity of the ionised gas (σ) is a function of the density of charged particles and,
consequently, of the frequency of ionising collisions. A coefficient α is widely used to express the
number of ionising collisions undergone by one electron in a 1 cm trajectory along the electric field E.
This is defined by the following equation [220]:
⎛ B ⎞
α ⎜⎜ − ⎟⎟
= Ae ⎝ E/p⎠ (5.1-2)
p
where α is Townsend first ionisation coefficient, p is the gas pressure, A and B are gas constants and E
is the electric field between the electrodes. A reduction in the pressure increases the E / p ratio and the
mean energy acquired by electrons between collisions, but it also reduces the probability of collision
with gas molecules, which defines the second constraint for equation 5.1-1.
Equation 5.1-2 resembles the experimental relation 4.1-2. Even though no clear physical meaning could
be attributed to each one of the constants, term C seems to account for the avalanche effect, while the
term on power P varies as σE (equation 4.1-1).
With regard to the bias, it is interesting to note that the real applied power differed from the bias set
point (figure 5.1-2). The deviations were considerable and erratic, although it can be said that at low
pressures there was a trend towards higher power levels than the set point, while at high pressures the
tendency was inverted. The data points for bias current, plotted against bias set point, lay in a straight
line, so that the control system is believed to calculate the bias from the current measured on the work
table (figure 5.1-3). This deviation is not considered to be of fundamental importance as long as it is
considered in the analysis.

No meaningful correlation could be found between the bias set point or the bias current and the
optimum treatment conditions at 125 Pa and 15% bias for ASPC, and 75 Pa and 10% bias for ASPN.
However, the applied power exhibits a very similar trend and the optimised treatment conditions
correspond to maxima in the applied power (figure 5.1-4). This is not surprising taking into account that
the electron density increases with the applied power [221]. At low pressure, the bias current saturates
and the power is thus limited, but higher power can be applied at moderate pressures. For current
densities low enough to avoid edge effects, the maximum applied power corresponds to the optimum
condition.
The optimised conditions for ASPC and ASPN also show some qualitative agreement with the Paschen
curves reported for pure H2§ and 25% N2 – 75% H2 [220, 222]. Pure H2 breaks down at higher
potentials and values of p·L (pressure x distance between electrodes) compared to the 25% N2 – 75%
H2 mixture. Furthermore, the ratio pLH2 / pLN2-H2 from the cited references gives an average value of
1.46, while the ratio of optimum pressures for this project pASPC / pASPN yields 1.66, which is in
reasonable agreement. This is a rather speculative interpretation, although it seems sensible to think of
the optimum working conditions found in this project as those closest to the point of highest ionisation
efficiency, i.e. the minimum in the Paschen curve [189].
Unfortunately, the full Paschen curves could not be obtained in the present project, thus only very
general conclusions can be drawn. In view of the experimental evidence, the curves are expected to
show a minimum breakdown potential in the region of the optimum treatment conditions reported here,
while they would be shifted to lower potentials and lower p·L values compared to the conventional DC
discharges, due to the additional influx of electrons from the metallic mesh of the AS furnace [223, 224].
§ The 3% CH4 content of the gas mixture used for ASPC does not significantly affect the plasma physicochemistry, so that it
will be considered as pure H2 for the purpose of this analysis.

In this regard, a comparison of the discharge parameters in DC and AS furnaces, making use of the
similarity relations [157], indicated the presence of additional charge carriers [190], i.e. the AS furnace
draws larger current and power than the DC furnace for similar discharge conditions (table 5.1-1).
Finally, figure 5.1-5 shows the same I-V characteristic curves of figure 5.1-1, but this time it includes the
value of E / p, represented in the size of the bubble. It is clear from this graph that electrons acquire
significantly larger energies in the low pressure side of the range of assessed conditions, which
accounts for the increased efficiency of the plasma treatment observed in this same pressure region.
2. Carbon expanded austenite
2.1. Layer growth kinetics
The results obtained by means of DCPC and ASPC showed substantial agreement in terms of layer
thickness, although differences were found depending on the ASPC treatment conditions (table 4.1-2).
An estimation of the carbon diffusivity was obtained making use of the following equation:
x = a(Dt )
1/ 2
= Kt 1 / 2 (5.2-1)
where x is the layer thickness, a is a constant, D is the carbon diffusivity, t is the treatment time, and K is
the product of a and D. The obtained values are listed in table 5.2-1 and they are in substantial
agreement with the values reported in the literature [118, 119, 225].
The measurements of layer thickness conducted after different treatment times gave some information
regarding the growth kinetics, as it is illustrated in figure 5.2-1. The data points obtained in this project
are plotted together with those reported by Y. Sun [118] and M. Tsujikawa et al. [119, 225]. The former

reported a linear dependence of layer thickness with the square root of time (equation 5.2.2) and
interpreted it as a proof of the dominance of atomic diffusion mechanism.
x = 3.80 + 5.95 ⋅ t 1 / 2 (5.2-2)
On the other hand, the data reported by Tsujikawa et al. [119, 225] show a quadratic dependence of
layer thickness with the square root of time, which agrees with the data points obtained in this project.
This trend has also been identified by other authors [226, 227] who attributed the deviation to the
sputtering of substrate material by highly energetic ions from the plasma.
One additional outcome of these assumptions is the existence of some incubation time for the layer
growth. The linear dependence reported by Sun has a non-zero ordinate at origin, which was
considered to be the consequence of adding methane to the gas mixture during the heating stage. In
contrast, the quadratic dependence found in this project, and also reported by Tsujikawa, indicates
some time will elapse before the layer starts growing, and this feature is of significance in order to
understand the mechanisms involved in the treatment.
To this end, it is generally accepted that expanded austenite forms under a metastable equilibrium of
carbon in austenite, sometimes referred to as paraequilibrium (PE) [110, 122, 147]. Leaving aside some
discussion on terminology [228-230], paraequilibrium can be defined as a kinetically constrained
equilibrium, in which the substitutional atoms are virtually immobile in front of the interstitial atoms [231,
232]. Other authors have interpreted PE as a complete trapping of interstitials in the substitutional lattice
[233] and, in the particular case of expanded austenite, the chromium content of the alloy seems to play
a fundamental role in trapping C and N interstitials [101].

Other trapping mechanisms of interstitial elements have been reported, which include interaction with
crystal defects [234]. Maalekian et al. [235] have recently studied the influence of a heavily dislocated
crystal structure on the distribution of carbon in martensitic steel, and Heure et al. [236] conducted
internal friction studies on ASS gas carburised at low temperature and concluded that the obtained
results were consistent with multicarbon interstitial-vacancy complexes. In the present study, COMs
were obtained on the same areas of a sample after different treatment times. Figure 5.2-2 shows the
average EBSD pattern quality and the carbon content from GDOES profiles, obtained after each
treatment. The pattern quality is sensitive to defects in the crystal structure [237] and a qualitative
correlation can be seen, although this evidence is not solid enough to draw conclusions.
2.2. Microstructure evolution
With regard to the microstructure, comparative studies conducted on AISI 316 after DCPC and ASPC
showed equivalent results. Figure 4.2-1 illustrates the change observed on the microstructure of AISI
316 after PC. The presence of slip bands has been previously reported [135, 238-240] and it is a clear
indication of plastic deformation of the surface layer under the high compressive stresses developed
upon the expansion of the austenite lattice. Contrary to what Xu et al. have reported [241], very short
incubation times were necessary in the present case, and slip lines were found in AISI 316 samples
after only 1 hour of plasma carburising treatment at 450ºC. The density of slip bands and the height of
the steps were observed to increase with treatment time.
The strain is obviously unevenly distributed, and depends on the crystallographic orientation of the
grains, relative to the stress plane [242]. In this way, some grains show no signs of deformation, while
others show one or two sets of parallel slip lines, i.e. one or two slip systems have been activated.
Moreover, a higher density of slip bands is seen close to the grain boundaries, whereas the central

region of the grain remains relatively unaffected (figure 5.2-3). This is the result of the stress
concentration and generation of dislocations at certain regions of the microstructure [243-245].
The rotation of the crystallographic structure upon plastic deformation is known to affect the texture of
ASS [246] and the anisotropic strain produced during plasma or ion beam surface treatments has been
found to produce rotation of the crystallographic planes of single crystal and polycrystalline samples
[247-249]. Several authors conducted XRD texture studies on plasma nitrided samples, and reported
differences in the pole figures obtained before and after the surface treatment [113, 250, 251]. Figure
5.2-4 shows the results obtained on PC samples in this project, which show good agreement with the
results reported by Mändl et al. [250].
The crystallographic structure of carbon and nitrogen EA has been extensively studied by means of
TEM and XRD, and there is a significant body of literature and discussion in this regard [106, 111, 114-
116, 252]. TEM studies provide extremely useful but also very localised information, and in the case of
XRD it is difficult to establish the individual contribution of different effects (residual stresses,
dislocations or stacking faults) [112, 114]. Therefore, an attempt was made to use EBSD and AFM to
provide complementary information on the microstructure of EA.
The slip bands in figure 5.2-5 exhibit some 40 nm steps, which are considerably larger than the 10 nm
limit reported for approximately 45% deformation in a similar material under tension [253]. The number
of emerged crystallographic planes can be estimated taking into account the relationship:
r r
h = nz ⋅ b (5.2-3)

r r
where h is the height of the step, n is the number of planes, z is the vector normal to the surface and b
the Burgers vector for the dislocations. Computations for the most common steps, about 30 nm in
height, yielded some 100 planes. Slipping was assumed to take place mainly along the {111} <110>
path, as this is known to be the main slip system in AISI 316 [242, 245, 246, 253].
The deformation mechanism proposed in [253] implies that the balance between the internal friction
necessary to move dislocations and the external applied stress (or the local stress field at a given stress
raising point) is reached at maximum deformation steps of 10 nm, equivalent to 52 emerging
dislocations. Consequently, if a direct comparison is considered valid, larger stress levels must have
been reached in the present project or the additional amount of dislocations generated by the plasma
diffusion treatment changed the equilibrium point.
The slip system activated in each grain, by the compressive plane stress developed during PC, depends
on the crystallographic orientation, as it can be seen in figure 5.2-6. Grains with one of the {111} planes
parallel to the surface are more prone to cross slip, although the angle of cross slip in some grains
indicate that sliding could have taken place on {100} or {110} planes, when their orientation was
suitable. The domains formed on cross slip, i.e. the chessboard like sub-grain arrangement [245], would
play a role of significance in the distortion and broadening of the XRD peaks, and could eventually
develop a deformation texture [246]. Although the inverse pole figures obtained with EBSD showed
some changes after the PC treatment, no consistent trend was observed.
The sub-grain structures are clearly visible after plasma carburising, and some sub-grain boundaries
can be seen from the line scans shown in figure 5.2-7. Moreover, the misorientation map also exhibits
signs of distortion (figure 5.2-8), and the grains with high density of slip bands also show large levels of

misorientation within the grain. It is speculated here that the small domains formed by cross slip rotate
upon deformation and they are thus responsible for the misorientation observed within the grains [246].
The AFM scans also indicate that these domains do not remain plane, but they are tilted during sliding
(figure 5.2-5). The changes in the colour orientation code of the EBSD COMs (sample normal direction)
indicate rotation of the crystallographic planes. Although attempts were made to quantify this rotation,
the results were not consistent.
The orientation relationship of grain boundaries was also affected by the plastic deformation, and the
change in Σ3 CSL grain boundaries is illustrated in figure 5.2-9. The degradation of CSL grain
boundaries with increasing strain has also been reported in [245], and it was found to be a consequence
of the rotation of the crystallographic planes away from the original CSL orientation relationship. Some
CSL were seen to degrade faster, presumably because those grains were suitably oriented for
deformation and rotation. However, this trend extended rapidly towards all the microstructure and grain
boundaries at longer treatment times and, consequently, larger strains.
2.3. Residual stresses (RS)
The assessment of residual stresses developed on AISI 316 PC samples has long been attempted, as it
has a considerable influence on the performance of this material. Several methods have been used to
measure residual stresses, and XRD is among the most accepted ones. Unfortunately, it was not
possible to use the XRD d-sin2ψ technique in this project, so alternative methods were used. However,
some comments will be made with regard to the XRD results obtained in the θ-2θ geometry.
After plasma carburising, the XRD austenite peaks were found to be consistently shifted to lower 2θ
angles and broadened, the latter effect increased with the reflection order. There exist a number of

different causes which could be responsible for these effects, and the determination of their individual
contributions usually involves some assumptions [249, 254]. Stacking faults and microstrains are
thought to be the main reasons for the peak broadening [107, 112], together with a reduction in the size
of the diffracting domains as a result of the considerable plastic deformation undergone during PC [255,
256]. The peaks are broadened very nearly symmetrically, so that twin faults seem to play only a minor
role [257-259].
The peak shifting can be associated with the high density of dislocations, twins and stacking faults, and
also with the level of residual elastic strains, i.e. residual stresses [107, 114, 257-259]. It is once again
difficult to separate the contribution made by each of these effects, but the XRD diffraction peaks (figure
4.2-10) and the plot of ahkl vs cosθ·cotθ (figure 4.2-11) are consistent with an uneven lattice expansion
(table 5.2-2) and the presence of high compressive residual stresses [107, 112, 114]. An attempt was
made to estimate the residual stress by using the method proposed by Wagner et al. [259]. This method
uses second order reflections to separate the contribution made by stacking faults and residual stresses
to the peak shifting. Thereby, the maximum residual stress estimated in this way was -1.98 GPa (refer
to Appendix C for details on this calculation).
The XRD measurements of residual stresses conducted by Sun et al. [254] on carbon EA yielded
average values in the order of -0.3 GPa to -1.5 GPa within the layer, with maximum compressive
residual stresses at the surface between -1.5 GPa and -3.5 GPa. These values were compared with the
maximum compressive residual stress from the expansion produced by the carbon content of EA,
calculated to be as high as -10 GPa, and plastic deformation was proposed to account for the partial
relaxation of such enormous residual stresses.

In this project, modified Stoney’s formulas were used to calculate the residual stresses developed
during PC, from the curvature of thin discs. Calculations yielded values of compressive residual stresses
in the order -0.4 GPa to -0.8 GPa, which are in considerable agreement with the average residual
stresses reported in [254]. The theory of thin plates and shells [260-262] was used to analyse the
bending discs further (refer to appendix C for details on these calculations). The average residual stress
obtained was -0.770 GPa, which is very close to the value obtained with the Stoney’s formula.
However, this calculation assumes a constant residual stress profile within the EA layer, which is far
from the real case. If the stress distribution is approximated by a triangular distribution (figure 5.2-10),
and reducing the moments to the layer-core interface, it yields a value of residual stresses at the surface
of -1.155 GPa. Furthermore, this triangular distribution of residual stresses is still fictitious. If the
hardening effect is considered to be a function of the carbon content of the EA, it is thus sensible to
assume that the residual stresses profile will be similar to the carbon-depth profile obtained from
GDOES. Figure 5.2-10 shows the distribution which, for the same input data used previously, gives a
maximum residual stress at the surface of -1.22 GPa.
These levels of stress are obviously higher than the yield stress of AISI 316 (240 MPa) so that a
significant degree of strain hardening must have taken place. It would be thus reasonable to presume
that the residual stresses are distributed according to the strain hardened profile [263]. Microhardness
tests are sensitive to residual strain [264, 265] and indentations conducted at different loads provide
information from different layers of material, depending on the penetration depth. The ratio of
indentation diagonal (D) to penetration depth (h) can be estimated to be approximately 7:1 [266]; and
empirical evaluations have shown that the contribution made by the first layers of underlying material up
to a depth equal to 3·h accounts for the 44% of the measured hardness [267].

Figure 5.2-11 shows hardness profiles calculated from LBC Vickers microhardness experiments,
considering the hardness values represent a layer of material equal to 1, 2 and 3 times the indentation
depth h. The hardness profile vs 3h is in reasonable agreement with the Knoop hardness profiles,
except for the outmost layer, where errors are known to increase for hardness measurements
conducted on cross sections. Considering a distribution of residual stresses equivalent to the curve
hardness vs 3h, the maximum compressive stress at the surface is found to be -1.61 GPa, in order to
produce the same bending moment as in the previous cases (figure 5.2-10).
The values of residual stresses obtained with this method are in surprisingly good agreement with the
ones measured by XRD. However, it must be said that the former method is expected to yield lower
values than the latter. The reason for this is that the bending discs give information about the residual
stresses of the first kind or macrostresses, whereas XRD measures microstresses [268].
Finally, the curves obtained by instrumented indentations will be briefly discussed from the point of view
of the residual stresses present on the samples. The indentations are affected by the presence of
residual elastic stresses and residual plastic strains, especially in the case of a material that work
hardens [269-271], and the shifting of the curves obtained from EA are consistent with the presence of
high compressive residual stresses (figure 4.2-15).
Unfortunately, the methodology used to estimate the residual stresses usually requires imaging the
indentation marks, and also the determination of some experimental coefficients, which could not be
done during this project. However, an attempt was made to calculate the residual stresses following the
methodology proposed in [272]. This method assumes the elastic response of the material is not
affected by the residual stresses, and so the shadowed area in figure 5.2-12 would represent the elastic

energy contribution of the residual stresses. Making use of some geometrical considerations with regard
to the indentor, the residual stresses can be calculated as follows:
P1 − P2
σ residual = (5.2-4)
2π tan 2 αh 2
where P1, P2 and h are obtained from figure 5.2-12 and α is an experimental coefficient. Substituting the
values in table 5.2-3, one obtains a residual stress of -9.57 GPa. This compares favourably with the
maximum theoretical stress of -10 GPa calculated by Sun et al. from the carbon content of EA, although
such a high level of stress is highly unlikely. The coefficient α could be a source of error, as this is
experimentally determined and the same value of α as in [272] was used in this calculation, without
further consideration. The method could thus yield some interesting results, although further
consideration of the experimental constants is necessary.
3. Tribological properties
3.1. Wear of AISI 316 untreated substrate
The evidence obtained on AISI 316 samples agrees with the results reported in the literature [52, 56, 57,
60, 61]. The rough appearance of the wear track (figure 4.4-4), the large size, shape and metallic nature
of the debris (figure 4.4-11) [273], the occurrence of strain induced martensitic transformation (figure
4.4-15) and the severe plastic deformation of the subsurface (figure 4.4-17) are all signs of severe wear
[274]. The plastic deformation of the subsurface and the formation of a fine microstructure in the
severely distorted layer of material are characteristic features of this wear regime. Moreover, the EBSD
COM revealed that this layer of material develops a strong deformation texture showing {111} or {100}
planes parallel to the surface (figure 5.3.1-1) [275, 276]

According to the theory of adhesive wear, the plastic flow of the subsurface is a result of the adhesion
between asperities at the sliding surfaces [62]. At the same time, some loose particles may become
embedded in one of the surfaces, and produce deformation and abrasion on the opposite surface [277].
The theory of adhesive wear is useful to explain such phenomena as subsurface deformation, transfer
of material to the counterpart slider and friction. However, this theory has been extensively challenged
because it fails to elucidate the mechanism of detachment of wear particles [274].
The theory of delamination has been developed to describe wear under conditions of subsurface plastic
flow [65, 278], and accounts for the formation of plate like wear debris particles, similar to the ones
found in this project [75]. The theory predicts the formation of subsurface voids, which would coalesce to
form cracks and, ultimately, to detach metallic debris particles. Although this theory has been
extensively used to analyse wear of metals [75, 274, 275, 279], other authors have questioned its
fundamentals, i.e. the nucleation of cracks in a region of the substrate which is essentially subjected to
high compressive stresses [280, 281]. These same authors proposed an alternative mechanism of wear
known as ratchetting.
According to the ratchetting wear mechanism, the fractures nucleated in the substrate are of ductile
nature, as a result of the severe plastic strain imposed by sliding. If the loads are low and the yield point
of the material is not exceeded, i.e. within the elastic range, the failure mechanism is most probably one
of high cycle fatigue [281]. On the contrary, if the yield threshold is exceeded, plastic deformation takes
place and accumulates in the subsurface region after each loading cycle. Consequently, the total strain
accumulated in the subsurface, after a number of loading cycles, exceeds the strain produced by each
individual loading cycle [280, 282] (figure 5.3.1-2). The latter scenario would lead to failure through a low
cycle fatigue mechanism, called ratchetting wear [281].

In both cases, i.e. delamination and ratchetting, the plastic flow accumulated in the subsurface plays a
fundamental role in the wear process. The understanding of the wear mechanisms of AISI 316 helps to
identify the cause of the significant increase in wear resistance observed after low temperature plasma
carburising. This will be further discussed in the following section.
3.2. Tribological properties of the expanded austenite layer
The plasma carburised specimens showed a significant improvement in tribological performance when
compared with the untreated AISI 316 (figures 4.4-1 and 4.4-3). Moreover, clear evidence of oxidational
wear mechanism was obtained from the appearance of the wear track (figures 4.4-4 to 4.4-6), the
appearance of the wear debris particles (figures 4.4-11 and 4.4-12) and their nature (figures 4.4-13 and
4.4-14).
Close observation of the wear tracks produced on PC specimens showed brittle failure of the outmost
layer of carbides (figure 5.3.2-1). This was very clear on samples with a thin EA layer, in which the brittle
carbide layer had very little or no support from the substrate [283]. On the other hand, the failure of the
outmost layer of carbides is not so clearly seen on specimens with thick EA layers. The carbides are
obviously removed upon wear, as the EA layer exhibits a very smooth surface with no signs of the
original particulate morphology (figure 5.3.2-2), but no evidence of spalling could be found on the sides
of the wear track. This can be attributed to the support provided by the underlying EA. In any case, the
outmost layer of deposited carbides does not seem to play a significant role in the wear resistance of
EA.
It is important to note that very little plastic strain is seen in the subsurface of worn PC specimens (figure
4.4-19). The deformation is mainly elastic, and plastic strain is only confined to the surface. The ratio of

elastic modulus to hardness (table 4.2-1) reflects this change, as it dropped from 105.75 for the
untreated substrate to 20.48 for the plasma carburised layer. Therefore, according to the theory of
ratchetting, the failure mode would change from low cycle fatigue (ratchetting) to high cycle fatigue
[281]. The predominance of this wear mode depends on contact mechanics considerations [85], namely
the normal load, the friction force and the roughness of the sliding surfaces. The maximum load a
specimen can bear without undergoing plastic deformation is a function of the EA layer thickness, and
failure of plasma carburised components has been reported at high loads, induced by the plastic
deformation of the underlying substrate material [129, 130].
In the case of a thick enough EA layer, or a low enough normal load, the stresses developed in the
subsurface are within the elastic range, and the wear process is limited to the surface of the specimen,
where a layer of oxide forms. The formation of this layer of oxides on the tribosurface is an indication of
a mild wear mode, which is commonly called oxidational wear [284]. The flow of heat is of significant
importance to this wear mechanism, as it defines the formation of the oxide layer. Additionally, different
types of oxide will be stable depending on the flash temperature, i.e. the temperature developed at the
contacting asperities [63]. In this way, haematite (α-Fe2O3) is reported to be the stable oxide at
temperatures below 300ºC, whereas magnetite (Fe3O4) is stable between 450ºC and 600ºC [58, 71,
284]. Regardless of the type of oxide, oxidational wear is a mechanism of mild wear.
The formation of the layer of oxide is thus of interest, in view of its relevance to the wear process, and
figure 5.3.2-3 shows the genesis of this layer. In the first place, small fragments are deformed under the
stress developed during sliding. It is important to note that these fragments may include WC particles
pulled out from the counterpart ball, as a result of the abrasion of the Co binder (figure 5.3.2-4) [285].
The fragments are subsequently compacted, to form a coherent layer, although the morphology of the

original particles is still visible on the oxide glaze (figure 5.3.2-5). Moreover, some fractures propagate
along the original deformation lines, as it is shown in figure 5.3.2-6. The development of fractures
perpendicular to the sliding direction is the first step in the detachment mechanism. The schematic in
figure 5.3.2-7 shows the different steps of nucleation and propagation of cracks until the final
detachment of wear fragments.
These observations are in agreement with the literature on wear of EA [128] and also with the
oxidational wear mechanism proposed in [59, 63, 284]. Furthermore, the layer of oxide, i.e. the
existence of a layer of material which is different from the original materials involved in the wear
process, is usually mentioned in the specialised literature as the third body. A further development of the
third body concept in tribological systems has been presented in [286] and involves a state of
equilibrium between competing mechanisms of detachment of particles from the surfaces and ejection
of particles from the contact region. In this way, the protective oxide layer is thought to grow up to a
critical thickness at which it becomes unstable and brakes.
Figure 5.3.2-8 illustrates the effect of the oxide layer thickness. Even though previous illustrations
clearly showed oxide particles underwent deformation during sliding, the thick oxide glaze was found to
fracture, in a way that resembled a brittle solid [274]. Consequently, the tough and thin oxide layer
seems to grow throughout the sliding process until a relatively thick oxide glaze forms, which finally fails
under the sliding asperities in a brittle manner. The role of the supporting layer must not be overseen,
and the mechanical properties of the underlying EA are of fundamental importance to support the
protective oxide layer, which would otherwise fail.

Therefore, the function of the layer of expanded austenite in the wear mechanism is, at least, twofold: it
reduces the plastic deformation of the subsurface and confines it to the surface, and it provides a
convenient support to the protective layer of oxides. Moreover, if a wear mechanism of abrasion or
microabrasion is taken into consideration, a third function can be added to the protective role of the EA
layer. In this case, the hardness ratio of the abrasive particles to the sliding surface is of importance
[129]. The principal abrasive particles in the system are Fe3O4 or α-Fe2O3 oxides (400-750 HV) [72,
274]. Thus, the cause of improvement becomes apparent as the hardness of the sliding surface is
increased from 200 HV to 800-900 HV, which is comparable or even higher than the abrasive particles.
With regard to friction, the interpretation of the friction force and friction coefficient is not unequivocal
and, additionally, there is a large scatter in the friction data reported in the literature for EA [141, 287-
290]. The results obtained in this project are in reasonable agreement with those reported in [128], i.e.
the EA layer exhibits some higher coefficient of friction compared to the untreated AISI 316 substrate.
This is consistent with the presence of a layer of rhombohedral α-Fe2O3 oxide, which is hard and
abrasive when compared to the more ductile cubic oxides, Fe3O4 and FeO [72, 291]. In addition, the
coefficient of friction increases with sliding distance until it reaches its steady state value, which could be
interpreted as an increase of the contact area upon the growth of the oxide layer [292]. Once the steady
condition is reached, the noise in the friction signal is a result of deformation processes, debris
detachment and debris ejection events [56].
4. Corrosion behaviour
4.1. Corrosion behaviour of AISI 316 untreated substrate in different acid solutions
The resistance of AISI 316 to sulphuric acid solutions is limited, and it mainly depends on the
temperature and concentration of acid in solution [30, 31, 37, 293]. In the particular case of the 16%

sulphuric acid solution at room temperature, the corrosion rate of this alloy is nil or very low, and the
attack is only concentrated on weak points in the microstructure, especially MnS stringers (figure 4.5-1)
[38]. However, on increasing the temperature of the solution up to its boiling point, the rapid evolution of
hydrogen makes AISI 316 active and severe corrosion occurs (figures 4.5-3 and 4.5-8) [2].
Addition of oxidising agents, such as Fe3+ and Cu2+ cations, substitute hydrogen in the cathodic
reactions, and consequently stabilise the passive film. This extends the range of corrosion resistance of
ASS to higher temperatures or higher acid concentrations [31]. From the electrochemical point of view,
the potential of stainless steel in these sulphuric acid solutions, with respect to a saturated calomel
electrode, has been reported to change accordingly (figure 5.4.1-1) [2, 37].
With regard to nitric acid, AISI 316 is generally passive under a wide range of conditions [37]. However,
highly oxidising solutions can produce transpassive corrosion, which is particularly intense at grain
boundaries (figure. 4.5-14) [294]. This type of attack develops sensitised grain boundaries, although it
also affects unsensitised boundaries to a lesser extent [2, 295].
4.2. Corrosion behaviour of carbon expanded austenite: outmost layer
The PC samples exposed to sulphuric acid 16% solution at room temperature exhibited very little
corrosion, and only the outmost layer of material was found to fail (figure 4.5-1). This early stage of
corrosion was confirmed during the tests conducted at boiling temperature, in which some material was
found to peal off the surface of the samples after only a few minutes of exposure. SEM and TEM studies
showed that the recovered fragments were of a similar nature to the outmost layer of material previously
studied (figure 5.4.2-1). The XPS analysis of this outmost layer yielded C, Cr, O and Fe peaks (figure

5.4.2-2), in agreement with the literature [36, 296]. Unfortunately, extensive use of XPS was not
possible during this project.
Further experiments conducted with polished samples, in sulphuric acid solution at room temperature,
showed good corrosion resistance in all cases. This clearly indicates that the corrosion resistance is not
a result of the deposition layer of carbides, nor of a thicker oxide layer formed upon plasma treatment
(figure 4.2-7). In a similar way as it was reported in [297], the primitive oxide layer was removed after
only a few minutes of exposure to the boiling solution of sulphuric acid. Thus, the carbon expanded
austenite was found to be corrosion resistant itself, and the passive film must have been formed, in-situ,
during the test.
The corrosion resistance of carbon, nitrogen and carbon-nitrogen expanded austenite has been
reported at length [96, 125, 132-134, 298-304]. Most of the evidence is in the form of polarisation curves
obtained in NaCl solutions and, in general, authors report:
A shift of the corrosion potential in the noble direction
Extended range for passivity
Complete suppression of pitting, even at very high anodic potentials
In some cases or under some conditions, considerably lower current densities
This description is in agreement with the results obtained in this project for corrosion in boiling sulphuric
acid solutions, namely: reduced evolution of hydrogen, extended range of passivity and lower corrosion
rates. However, the underlying passivation mechanism is still an open question.

An electrochemical study of surface modified ASS with nitrogen and carbon reported benefits in terms of
corrosion resistance, but the experimental details are sparse [305]. The reported mechanism of
dissolution of nitrogen and alkalisation can not explain the good response of the carburising layers [306]
cited in [307]. More recent studies have proposed different mechanisms of passivation, including salt
passive films [308, 309], hydrated oxides [307], modification of the semiconductor characteristics of the
passive film [303] or even the same corrosion mechanism as in the untreated substrate [304].
Unfortunately this remains unclear.
4.3. Defects in the expanded austenite layer [310]
In reducing solutions, under cathodic potentials (figure 5.4.1-1), the improvement in corrosion resistance
is significant. The evolution of hydrogen is not so readily observed after immersion, and the expanded
austenite clearly shows a wider window of passivity, when compared to the untreated AISI 316
substrate (figure 4.5-8 and 4.5-9). The improvement is limited by the susceptibility of EA layers to
localised corrosion on weak points of their structure (figures 4.5-4 to 4.5-6). These are clearly developed
in more oxidising environments, such as sulphuric acid solutions with Fe3+ and Cu2+ additions, and also
in nitric acid solutions (figures 4.5-11 and 4.5-14). The latter solutions shift the potential of ASS in the
anodic direction and render it passive, so that very mild or negligible general corrosion of the grain
surface occurs, whilst the dissolution of susceptible areas is accelerated, thus increasing contrast [295].
Elongated MnS stringers reaching the surface are known to diminish the corrosion resistance of surface
alloyed ASS [142], and the attack progresses very rapidly after immersion in the boiling sulphuric acid
solution (figure 4.5-4). The presence of slip bands evidences plastic deformation taking place during the
treatment as a result of very high compressive stresses developed by the expansion of the austenite
[238]. These defects, together with some susceptible grain boundaries, are preferential sites for

precipitation of carbides (see next section) and they provide channels for the corrosive medium to reach
the substrate, where subsurface pits are formed (figures 4.5-5 and 4.5-6) [311].
Consequently, it can be said that corrosion of PC specimens is controlled by the density of defects in
the expanded austenite layer. Figure 5.4.3-1 shows a schematic of the failure modes observed on
treated samples. The most intense attack takes place on MnS inclusions, but localised corrosion also
occurs on slip bands and grain boundaries. Corrosion progresses at a continuous rate, depending on
the type of defect, until the substrate material is exposed. At this stage, a rapid anodic dissolution of the
substrate takes place and subsurface pits of significant size are formed. In areas where the density of
defects is high, the subsurface pits coalesce and the expanded austenite layer flakes off. In applications
involving corrosion-wear, the formation of cavities in the subsurface layer would significantly affect the
performance of the components [312, 313].
The density of slip bands and of susceptible grain boundaries is higher at the edges than in the central
area of the specimens (figure 5.4.3-2). Furthermore, the density of these defects increases with the
applied power (i.e. ASPC 030, ASPC 125 and DCPC 400 in increasing order). This is attributable to the
strong plasma-surface interactions developed on sharp edges, and the associated local increase in
current density and temperature. The bias levels, thus the power and current densities, selected for
each ASPC treatment account for the observed differences in corrosion performance. In this way, low
bias levels produce uniform surface morphologies on the treated samples and, consequently, a more
even and predictable corrosion behaviour is observed. On the other hand, high bias levels and,
ultimately, DCPC produce edge effects, and the consequent uneven or localised corrosion.

4.4. Effect of deformation and precipitation of carbides
The slip bands observed on the PC samples are non-equivocal evidence of plastic deformation taking
place during the treatment, presumably due to the high residual stresses developed upon the expansion
of the austenite unit cell. The dislocation walls so formed can become subgrain boundaries (figure 5.2-7)
[245]. Moreover, due to the constraints imposed by the neighbouring grains, plastic deformation usually
implies some degree of rotation of the crystallographic planes, as it has been reported in deformation
studies conducted in ASS [242], and also for EA [247-249]. This rotation has a significant effect on the
type of grain boundaries and can, eventually, lead to the development of a deformation texture [245,
246]. Finally, precipitation of carbides is also affected by deformation structures and grain boundary
characteristics [20, 24, 314]. All these features —namely crystallographic texture, grain boundary
characteristics and precipitation of carbides— have a marked effect on the corrosion properties of ASS
and will be discussed below.
The effect of crystallographic texture on the corrosion resistance of ASS was reported in [44], where
closely packed crystallographic planes were found to favour the formation of the passive film, and
reduce the amount of sites for localised corrosion, with the consequent increase in corrosion resistance.
In this project, even though deformation took place, no significant deformation texture seems to have
developed (figure 5.4.4-1). The changes in the inverse pole figures obtained on untreated AISI 316 and
on PC showed no consistent trend, so that texture can not be considered to contribute significantly to
the corrosion resistance of EA. Furthermore, the quantity of favourable sites for localised corrosion is
greatly increased in EA layers.
With regard to the grain boundaries, several studies have recently reported improvements in corrosion
resistance of ASS through an increase in the number fraction of special grain boundaries and a

reduction in the connectivity of random grain boundaries [45, 46, 315]. However, the trend observed in
this project is towards a degradation of CSL orientation grain boundaries (figure 5.4.4-2), which are
converted into stepped boundaries as reported in [245]. This supports the results reported in [316],
where an increase in corrosion resistance was obtained by increasing the frequency of random grain
boundaries. The postulated mechanism is related to the flux of chromium and the precipitation of
carbides of small size only, which will be discussed in what follows.
Precipitation of chromium carbides is of significant importance to the corrosion resistance of ASS since
it produces a depletion of chromium in the surrounding areas, and the consequent weakening of the
passive film. This process is mainly dependent on the diffusion of chromium and, consequently, on
temperature [314], thus sharp corners are more susceptible to exhibit precipitates due to the edge effect
developed on them (figure 5.4.4-3). However, the deformation structures have been found to play an
important role in carbide precipitation and the high energy grain boundary ledges produced on
intersection of grain boundaries with slip bands, or even the intersection of two slip bands seem to offer
favourable sites for precipitates [19, 314, 317, 318]. Moreover, recent studies have reported early
stages of precipitation at temperatures as low as 250ºC [319]. With regard to carbon expanded
austenite, precipitation of small needles of M5C2 carbides have been reported to be favoured at
crystallographic defects, where diffusion of substitutional elements (mainly Cr and Ni) requires minimum
energy [121, 123].
In this project, evidence of carbides has been obtained by means of XRD, TEM (figure 4.2-8) and EDX
(figure 4.5-13). Furthermore, the selective attack observed in corrosion experiments is consistent with
the type of sensitisation reported in [320] associated with precipitation at deformation structures. Given
the high carbon content of the EA, the presence of favourable sites renders precipitation of carbides

highly probable [20, 24]. However, the low temperature at which the treatment is conducted only allows
short range diffusion of substitutional elements, so that the chromium depletion is of a local nature, thus
severe intergranular corrosion is avoided.
5. Plasma diagnostics: Optical Emission Spectroscopy (OES)
5.1. Plasma chemistry
The spectra in figures 4.6-1 to 4.6-3 show the typical optical emission peaks obtained for gas mixtures
corresponding to nitriding, carburising and nitrogen enhanced carburising. Although the existence of N
and C containing species is essential for these surface treatments, the presence of other species —
either as pollutants, as by-products of a primary reaction, or as intentional additions to the gas mixture—
can have a non-trivial effect in the physicochemistry of plasma. Some of these reactions are considered
of importance for the interpretation of the OES results obtained in this project and will be discussed in
the following paragraphs.
Plasma nitriding in N2-H2 and in N2-H2-Ar gas mixtures have been extensively studied and a large
amount of evidence has been gathered [165, 321-327]. The effect of Ar and H in depassivation and
surface activation is usually highlighted. In the case of Ar, this is achieved through increased sputtering
power of the gas mixture, whereas H increases the chemical etching of O species. Moreover, the
dissociation of N2 is increased with small additions of H2 (less than 1%), which was attributed to the
strong interaction (population and depopulation) between vibrational levels of both molecular gases
[328-331]. The electric parameters of the discharge also vary with increasing H2 content of the gas
mixture, and a minimum in discharge impedance is found around 75% N2 − 25% H2.

In the case of carburising, there is significantly less information available [332], although the CH4-H2 and
CH4-H2-Ar plasmas have been extensively studied for deposition of diamond-like carbon [333-338]. In
these studies, atomic H has been clearly identified as a by-product of the decomposition of the CH4
molecule. In addition, a role of significance has been assigned to atomic H in the dissociation of CH4
[336, 337]. Depending on the gas pressure and gas temperature, dehydrogenation of methane by H
atoms competes or even dominates over electron impact dissociation.
The hydrogen abstraction efficiencies of CO and OH have been reported to be even higher than atomic
H [338, 339]. Bearing in mind these same principles, and due to technical limitations to do experiments
with other gases (CO, CO2 or O2), small additions of N2 were used. Contrary to what could be expected
from the dissociation enthalpies listed in table 5.5-1 [340], a strong interaction between N and C is
evident from the relatively high activity of CN groups in figure 4.6-2. The interaction between C and N to
form CN species has also been reported in [341], and this mechanism would involve a chemical driving
force, similar to the one reported in [339] for dissociation of CH4 with small additions of CO. This result
highlights the importance of chemical interaction between the species present in the plasma phase.
5.2. Emission intensity maps
The emission intensity maps obtained by means of the optical fibre probe yielded good information on
the plasma under different treatment conditions (figure 4.6-5). The selection of the emission bands used
for the purpose of the emission intensity maps was very much influenced by the signal-to-noise ratio.
However, there are good reasons to correlate these bands with the N and C activity in the plasma. In
the case of nitriding, transition N2+ (B2Σu+ − X2Σg+) is usually the most intense, with a band head at
391.44 nm [342, 343]. Moreover, this so called first negative system of N2 has been related to

vibrational metastable states [344], which are believed to play a significant role in the stepwise
dissociation of molecular nitrogen, in view of the high energy required for direct dissociation [345, 346].
The emission intensity is known to increase with the electron density (ne) and the electron temperature
(Te) and, as a consequence, the emission intensity increases with the power (figure 4.6-6) [347]. The
electron temperature is particularly important, assuming that ionisation takes place mainly through
single collisions with energetic electrons. However, for a molecular gas, and in particular for N2, step
ionisation from excited levels must also be considered [348-351]. An example of stepwise excitation
proceeds as follows:
e − + N 2 ( X ) → e − + e − + N 2+ ( X ) (5.5-1)
e − + N 2+ ( X ) → e − + N 2+ (B ) (5.5-2)
where X indicates the ground state and B the excited state, and this or similar mechanisms would be of
importance at high electron densities and low electron temperatures. This is believed to be the case at
the high pressure range assessed in this project (P > 250 Pa), where the electron temperature has been
reported to drop due to the increasing number of collisions, and the electron energy distribution function
shows a significantly smaller high energy tail [222, 352-356].
Figure 5.5.2-1 illustrates the relative increase in the emission intensity of the nitrogen first negative
system, with respect to the hydrogen Balmer series, at increasing gas pressure in ASPN conditions.
Considering the energy required for direct electron impact excitation of Hα and N2+ are 12.74 eV [346]
and 18.5 eV [357] respectively, it seems plausible that, in the high pressure range, the N2+ is being
populated through stepwise ionisation, which lowers the energy threshold to 10.5 eV [357]. Moreover,
these changes in the electron energy distribution function (EEDF) and the ionisation processes with gas

pressure could also account for the different trends observed in the emission intensity with respect to
discharge electric parameters (figure 4.6-6).
In the case of ASPC, the absence of intense peaks corresponding to C containing species limits the
analysis to the hydrogen Balmer series. As it was mentioned in section 5.1 of this chapter, atomic
hydrogen is not only a by-product of the decomposition of the methane molecule, but it also plays an
active role in the dehydrogenation of CHX groups. Therefore, its study could be considered to represent,
to some extent, the C activity in the plasma. Nevertheless, the study of CHX emission peaks in the
vacuum UV region of the spectrum, or in absorption, would be of interest [358].
The intensity maps obtained under carburising atmospheres (figure 4.6-5) exhibit one interesting
feature: in the low pressure region, the emission intensity was found to increase with the applied bias up
to a maximum value, near the current saturation region, followed by a marginal decrease on further
increasing the bias. This was contrary to the expectations, as higher applied power was supposed to
yield higher emission intensity. The trend was initially considered an experimental error, but the same
phenomenon was observed on repetition of the experiment in CH4-H2 gas mixtures, although it was not
so evident or not observable at all, in N2-H2. A possible explanation for this phenomenon became
apparent from the results of the ion flux probe, discussed in the next section.
6. Plasma diagnostics: Ion flux probe (IFP)
The flux of ions measured in the AS industrial furnace under both nitriding and carburising atmospheres
shows the same trend, i.e. the ion flow increases with the bias level, and decreases with gas pressure
(figures 4.7-5 and 4.7-6). The effect of bias seems self-evident, as an increase in the negative potential
applied to the worktable increases the electric field, thus the ion drift. In the case of pressure, two

different effects merge together: the reduction in the ion mobility on increasing pressure, and the
changes in the EEDF which affect the production of ions, as discussed in the previous section [220].
The trend followed by the floating potential of the probe (i.e. the potential at which equal number of
electrons and ions arrive at the probe, thus yielding zero net current) is noteworthy. The floating
potential initially dropped to more negative values when bias was applied, followed by a reverse in the
trend on further increasing the bias, and this behaviour was clearer in CH4-H2 than in N2-H2 gas
mixtures (figure 4.7-4). Although the phenomenon was initially considered an artefact, its resemblance
to the OES observations raised doubts.
On further analysing the OES and IFP signals and the electric parameters of the AS furnaces during the
experiments, it was found that the reduction in emission intensity and the shifting of the floating potential
to more positive values, correlated with considerable reductions in the power applied to the mesh of the
AS furnace. This reduction was imposed by the automatic control system of the furnace in order to keep
the temperature stable, to compensate for the increasing power applied on the worktable. In view of
these observations, the cathodic mesh in the AS furnace could be considered an additional source of
electrons, similar to the triode discharges reported in [359-361].
With regard to the measurements conducted with the electric probe in DC and AS experimental
arrangements inside a conventional DC furnace, similar trends were observed: the AS arrangement
produced larger ion fluxes, and changed the floating potential (figure 4.7-2). However, the latter varied
depending on the gas mixture. For the carburising atmosphere, the floating potential dropped to more
negative values, whereas under nitriding atmospheres the potential shifted in the positive direction.

Considering that the same gas mixture, the same gas pressure, and the same electric discharge
parameters were applied in both the DC and the AS experiments, the electron temperature is thought to
remain constant. Therefore, the differences may be attributed to an increase in the electron density,
which is, once again, consistent with the results reported for triode discharges [359-361]. In the
particular case of nitrogen containing atmospheres, higher electron densities would render step
ionisation processes more profuse, thus increasing the density of ions and shifting the floating potential
to more positive values (i.e. less negative floating potentials are required to balance the flow of electrons
and ions).
However, there is an additional factor that should be considered in the case of an AS furnace, namely
the geometry of the cathodic mesh. The mesh in an AS arrangement is negatively biased and it
surrounds the workload, so that there is an electric field which tends to confine electrons within the
operative volume of the furnace. This concept is by no means new, and there is a large body of
literature on the electrostatic confinement of plasma in a variety of ways, and using different electrode
arrangements [221, 223, 362-367].
A considerable increase in the plasma density is reported by confining charged particles, as the path of
electrons from the cathode to the anode is extended due to reflections on the cathodic surfaces [223,
362]. The confinement effect is restricted to the low energy electrons (slow or cold electrons), whilst the
high energy electrons (fast or hot electrons) would escape the trapping electric field [366]. The
dimension and the geometry of the chamber are of significant importance in this regard. Furthermore,
the confinement is consistently reported to be more effective in the low pressure range [221, 363, 365],
in which the negative glow extends to fill the whole volume within the confining field.

The creation of a uniform negative glow throughout the operating volume of the furnace is of interest
because it is in this region of the gas discharge where the active species are produced. Therefore, the
high electron density developed inside the mesh of an active screen furnace facilitates the creation of
active species. Furthermore, the electron density has already been proposed as a parameter to predict
and control the carbon potential of the plasma [171]. Consequently, the parameters of the electric
discharge affect the chemistry of the gas (increase activity through ionisation), and this, at the same
time, affects the parameters of the electric discharge (changes in EEDF observed in molecular gases).
As a result, both parameters should be considered together [368].
It is thus proposed that the AS arrangement contributes to the creation of additional primary electrons
and confinement of charged particles within the operative volume of the chamber, yielding plasma
conditions more suitable for nitriding and carburising. The electric parameters applied on the workload
can be thus controlled independently to produce the required degree of ion bombardment on the
components [359-361, 369].
7. Mechanisms of active screen plasma surface engineering
It is convenient to begin the discussion on the mechanisms of active screen plasma surface engineering
by talking about nitriding, as this has been more extensively studied than carburising. The evidence
found in the former will be comparatively discussed with respect to the latter.
7.1. Active screen plasma nitriding (ASPN)
One of the most interesting findings of the experiments on the mechanisms of active screen plasma
surface engineering is the layer of material deposited on the ASPN treated samples (figure 4.3-7). This
deposition layer covered the AS plasma nitrided specimens with a morphology that depended on the

treatment conditions and the crystallographic orientation (figures 5.7.1-1 and 5.7.1-2) [370]. The glass
slides were especially useful for XRD studies (figures 4.3-10), and the pattern shows a very clear
coincidence with FeXN nitrides and a remarkable correlation with FeN (figure 4.3-11). This experimental
finding is of significance considering that the deposition layer has been deemed in the literature as one
of the fundamental mechanisms of active screen plasma nitriding [181-183].
The sputtering and redeposition mechanism was first proposed by Kölbel and has been supported and
reviewed by several authors ever since [154, 159, 160, 371, 372]. The model attributes the nitriding
mechanism to iron atoms which are sputtered from the specimen, and subsequently react with the
nitrogen in the plasma. Unstable FeN nitrides would thus be redeposited on the specimen surface, and
would decay into lower Fe2-3N and Fe4N nitrides, releasing nitrogen atoms free to diffuse (figure 5.7.1-
3). In the case of active screen plasma nitriding, the mesh was proposed to be the source of sputtered
iron atoms [181-183], in view of the absence of ion bombardment or sputtering on specimens treated at
floating potential [179].
Further evidence on the importance of the transferred material is apparent from the results obtained
under an AS arrangement using a mesh with big holes. In the case of ASPN, the area of the sample
covered by the mesh exhibited significant hardening effect, while the area under the hole showed little
signs of nitriding (figure 4.3-6). The appearance of both areas of the sample is very similar, and only a
minor change in the metallic shine is observed, the area covered by deposited material being dull grey,
whereas the area under the hole retained its metallic shine. In terms of composition, the EDX analysis of
the deposited material revealed alloying elements such as Cr and Ni in addition to Fe (figure 5.7.1-4), in
agreement with the composition of the AISI 304 mesh (figure 4.3-12).

Sputtering of material from the mesh and its subsequent deposition on the treated specimens has been
extensively discussed and reported in the literature on active screen plasma nitriding [180, 373-376]. To
this end, and given the evidence produced during this project, sputtering and deposition is an irrefutable
fact, although its relevance for the treatment is still an open question, and it has been seriously
confronted [185, 377]. The results obtained in this project indicate that the treatment conditions for the
thickest deposition layer of iron nitride differ from those ones for the thickest layer of nitrogen expanded
austenite (figure 5.7.1-5). Indeed, the very concept of active screen plasma nitriding was not developed
on the theory of sputtering and redeposition, but on the post-discharge nitriding, i.e. the generation of
active species on the mesh and their transfer to the worktable through a carefully designed gas flow
[177].
From the experience gathered in this project, the contribution made by the gas flow to the transfer of
active species from the mesh towards the worktable is arguable. This is evident considering that
experiments conducted inside DC furnaces have been widely successful without introducing any special
modifications in the gas flow [180-183, 374, 378]. Furthermore, experimental arrangements with plate
lids, which severely restrict gas flow, have produced similar or even better results than those with mesh
lids [182, 378]. In addition, the distance active species can travel as such, is limited due to their
considerably short lifetimes. This was observed in the experiments conducted without a lid in [182] and
also in the experiments conducted in this project using a mesh with big holes, in which the hardening
effect was limited to regions of the specimens lying in proximity to the active screen mesh (figure 4.3-6).
Consequently, the post-discharge mechanism seems to be limited to relatively small scales and, in fact,
it has been found difficult to produce satisfactory hardening in large scale active screen units without
applying some level of bias on the treated components [184, 185, 377, 379]. Nevertheless, the

relevance of the mesh as a source of active species deserves further attention. In this project, the
efficiency of the plasma treatment showed a substantial degree of correlation with the optical emission
intensity of active species. At the same time, the emission intensity was affected by the electric
discharge conditions on the mesh. Consequently, the influence of the mesh on the treatment becomes
apparent, and it is here proposed that the role played by the mesh in an AS furnace is threefold: it
radiates heat, it is an additional source of electrons in a similar way to a triode discharge; and it confines
electrons within the operative volume of the furnace.
These last two roles of the mesh in an AS furnace are not mutually exclusive, but synergetic. The
beneficial effect of an additional source of electrons has been reported in experiments conducted in
triode discharges [359-361] and was discussed in a previous section. However, it has also been noted
that the plasma density is not uniform in these arrangements [380]. On the contrary, the geometrical
arrangement of active screen furnaces produces an even distribution of electrons around the workload.
Furthermore, under suitable conditions, the confining negative electric field generated by the mesh
would also contribute to produce a higher electron density and more uniform distribution of electrons
and, as a consequence, a more uniform plasma density [223, 362, 363].
The theory is consistent with the results obtained in this project, and those ones reported in the literature
on active screen [185], triode discharges [359, 360] and electrostatic confinement of plasmas [223, 362,
363]. The additional electrons provided by the mesh allow operating the furnace at lower pressures, at
which the electrostatic confinement is also more effective. The higher electron density implies an
increased number of collisions with gas molecules, which will eventually lead to a larger number of
active species and a higher plasma density. This can finally be translated into an increased plasma
reactivity and nitriding power.

A final comment should be made on the need to apply bias in large scale active screen units [184, 185,
379]. This issue recalls the ancient discussion on the effect of ions versus the role of neutrals in plasma
nitriding [381-383]. The equipment used in this project did not allow for a complete decoupling of the
voltage and current discharge characteristics of the worktable, which are related with the ion energy and
ion flux. Therefore, the results are not conclusive, although there is a clear increase in the hardening
effect and the EA layer thickness with both increased voltage and current, i.e. with increased applied
power.
Even though it was possible to nitride samples at floating potential, this condition did not produce the
thickest layer of EA. Furthermore, the adhesion of the deposition layer was not satisfactory and the layer
of iron nitrides was found to peel off in some regions (figure 5.7.1-6). It can be thus concluded that a
small level of bias is not only desirable, but also necessary to optimise the treatment conditions. The
deposition layer seems to be beneficial, but it is not the only mechanism operating in ASPN treatments.
The evidence indicates that the active species in the plasma are of fundamental importance to control
the nitriding potential. Therefore, the optimisation of the treatment would require uncoupling the plasma
generation and heat source from the treated components [361, 380], and carefully selecting the
discharge conditions applied on the worktable, in order to favour the plasma-surface interactions, which
are of complex nature [323].
7.2. Active screen plasma carburising (ASPC)
The results obtained for AS plasma carburising indicate similar trends to AS plasma nitriding, although
the operating mechanisms are clearly different (figure 4.3-10). The first significant distinction observed is
the complete absence of a coherent and dense deposition layer. The glass slides treated in ASPC
conditions only exhibited some fine powder on their surfaces which, according to the EDP obtained in

TEM studies, was identified as Fe3C (figure 5.7.2-1). Further characterisation of this material was only
possible from the deposition film grown on the walls of the furnace —i.e. on the anodic walls lying some
100 mm in front of the cathodic mesh— after several consecutive carburising treatments. The
morphology is obviously coarser (figure 5.7.2-2), but it is clearly formed by conglomeration of smaller
particles, and the XRD result indicates a very good correlation with the Fe3C pattern.
A thin layer of carbides was found on ASPC treated AISI 316 samples (figure 4.2-8), and it has been
reported in the literature [384]. However, the role of these carbides in the mechanism of plasma
carburising treatments seems to be negligible. Therefore, plasma carburising seems to arise as a result
of the step decomposition of the methane molecule according to the following reactions [163, 385]:
e − + CH 4 → CH 3+ + H + 2e − (5.7-1)
e − + CH 3 → CH 2+ + H + 2e − (5.7-2)
e − + CH 2 → CH + + H + 2e − (5.7-3)
e − + CH → C + + H + 2e − (5.7-4)
The ions would thus be adsorbed at the cathodic surface and would release C atoms free to diffuse into
the bulk material. The fact that CH and C ions or excited species were not abundant in the OES spectra,
collected during the ASPC treatments, leads to the assumption that CHX species with x > 1 would be
responsible for the hardening effect. This assumption implies that a significant amount of hydrogen is
adsorbed with the carbon, which was suggested in [386] and confirmed in [387].
The quantity of reports on plasma carburising is sparse, although there is a high degree of agreement in
the evidence. In general, the carburising is attributed to reactions under electric control, which

emphasises the importance of plasma activation and plasma reactivity [155, 332, 388]. A direct
correlation between ions and excited species, and the carbon mass flow has been established;
moreover, the electron density has been proposed as a convenient variable to control the carbon
potential of the plasma [171]. All this evidence is in favour of the model proposed for AS plasma surface
engineering, in which higher electron densities would increase the number of collisions and the plasma
reactivity.
However, this explanation is not completely satisfactory in view of the difficulty to produce hardening on
samples left at floating potential. This was initially thought to be a consequence of the presence of
passivating oxide at the surface of AISI 316 specimens. Therefore, some experiments were conducted
applying a surface activation stage at the beginning of the treatment, consisting of bombardment of the
surface with argon ions, but the results were equally negative. Furthermore, the high hydrogen content
of the gas mixture is supposed to chemically etch the oxides formed on stainless steel samples, and to
increase the tolerance of the treatment to residual oxygen gas [388]. Nevertheless, the results were
negative in all the attempts, thus it can be concluded that the application of bias is essential for ASPC.
The equipment used in this project did not allow for an independent selection of potential and current,
but the hardening effect was found to increase with both, i.e. with the applied power.
This need for ion bombardment to produce hardening in H2-CH4 gas mixtures does not weaken the
potential benefits offered by the AS technique. The uncoupling of the plasma and heat sources from the
treated components, provides an additional degree of freedom to optimise the treatment. Furthermore,
the possibility to increase the electron density, the plasma density and the plasma uniformity within the
operative volume of the furnace, is clearly an interesting feature of AS. Finally, the transfer of material

from the mesh onto the worktable was negligible in the case of ASPC, compared to ASPN. This
discards the sputtering and redeposition as a main mechanism for ASPC.

CHAPTER 6: SUMMARY AND CONCLUSIONS
The evidence produced throughout this project and the discussion presented in the last chapter can be
summarised as follows:
I. Active screen plasma processing:
1. It is possible to generate carbon expanded austenite in austenitic stainless steel using active
screen plasma technique.
2. Based on systematic experimental work, effective AS processing windows have been identified to
produce carbon and nitrogen expanded austenite equivalent to conventional DC treatments.
3. Optimal treatment conditions for maximum layer thickness and no incidence of edge effect were
identified at 125 Pa and 15% bias for ASPC, and 75 Pa and 10% bias for ASPN.
4. The surface quality of active screen treated samples could be significantly improved compared to
the DC counterparts. Defects such as edge effects, hollow cathodes and arcing were minimised
or eliminated.
II. Characterisation of carbon expanded austenite produced on AISI 316:
5. The layer of carbon expanded austenite produced in the active screen furnace was equivalent to
the one obtained in DC furnaces in terms of layer thickness, composition, phase constitution and
hardness. Improved surface quality was consistently obtained under the right AS treatment
conditions.
6. The microstructure of the treated material was severely deformed and distorted. Degradation of
the CSL boundaries took place, with a trend towards a randomisation of the grain boundaries.
Chapter 6: Summary and conclusions Page 132

7. The residual stresses developed in the plasma carburised layers were measured and the
maximum compressive residual stresses were calculated to be in the order of -1.6 GPa. Residual
stresses were found to increase with the ion bombardment and the layer thickness.
III. Tribological properties of carbon expanded austenite:
8. Under the conditions assessed in this project, plasma carburised AISI 316 exhibited a resistance
to wear two orders of magnitude higher than the untreated material.
9. The dominant wear mechanisms were found to be changed from severe adhesive and
delamination wear for the untreated AISI 316, to mild oxidational wear for the plasma carburised
material.
10. The carbon expanded austenite can avoid subsurface plastic deformation, increase resistance to
abrasion by hard particles or asperities, and provide support to the protective oxide layer.
11. The coefficient of friction exhibited by carbon expanded austenite was higher than the untreated
AISI 316 under the sliding conditions used in this project.
IV. Corrosion behaviour of carbon expanded austenite:
12. Plasma carburised AISI 316 showed higher corrosion resistance than the untreated AISI 316 in
boiling 16% sulphuric acid solutions. Furthermore, active screen plasma carburising produced
greater improvement than DC treatments through the elimination of edge effects.
13. The outer layer of carbides played no protective role against corrosion, but it failed shortly after
being immersed in acid solutions. The improved corrosion resistance was attributed to the carbon
expanded austenite itself.

14. The failure of the carbon expanded austenite in a corrosive environment was defect controlled.
The weak points of the microstructures include: MnS inclusions, deformation slip bands and grain
boundaries. Sharp edges were particularly susceptible areas to develop the latter two defects.
V. Plasma diagnostic techniques:
15. Optical emission spectroscopy, in the UV-visible range, was a valuable technique to identify
active species in N2-H2 gas mixtures, although it was severely limited in the case of diluted CH4-
H2 atmospheres.
16. The emission intensity of nitrogen ionic species and hydrogen atomic species showed a
considerable correlation with the treatment effectiveness. Therefore, the intensity maps obtained
with the optical fibre probe were useful to identify the optimum range of treatment conditions.
17. The interpretation of the ion flux probe signal indicates that the plasma inside an active screen
furnace was considerably affected by the electric parameters applied on the cathodic mesh. The
flow of ions increased with increasing bias and decreased with increasing gas pressure.
VI. Mechanisms of active screen plasma surface engineering:
18. Sputtering and redeposition was found to be a mechanism of significance for active screen
plasma nitriding, although the active plasma species and some moderated ion bombardment
were necessary for treatment optimisation.
19. Ion bombardment was a necessary condition for active screen plasma carburising. The activation
provided by the plasma was of importance for the decomposition of methane, whereas sputtering
and redeposition played no role in this case.
20. The role of the cathodic mesh in an active screen furnace seems threefold: it radiates heat, it is
an additional source of electrons in a similar way to a triode discharge; and it confines low energy

electrons within the operative volume of the furnace in a manner that resembles an electrostatic
confinement of the plasma.

CHAPTER 7: PROPOSALS FOR FUTURE WORK
The present project contributed to the understanding of active screen plasma processing, the
characterisation of carbon expanded austenite, its tribological properties and corrosion behaviour.
Evidence was produced on the mechanisms involved in the active screen plasma treatments, and the
diagnostic techniques allowed some basic characterisation of the plasma. From the results obtained in
this project, the following topics are suggested for future studies:
The metallic mesh of AS furnaces may be replaced by other electrode arrangements, which
could be equally or even more effective in producing additional electrons and plasma
confinement, and show further flexibility and simplicity, e.g. segmented hollow cathodes.
Plasma diagnostic with optical fibre assisted OES and electric probes provide useful and
complementary information about the plasma. Further improvements of these techniques would
be valuable, for example to produce spatial distribution maps of active species, electron density
and electron temperature inside the AS furnace.
Chapter 7: Proposals for future work Page 136

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TABLES
Table 2.3-1: Typical commercial ASS compositions [4]

Composition [wt%]
AISI type
301 302 304 310 316 321 347
Element
C 0.15 max 0.08 max 0.08 max 0.25 max 0.08 max 0.08 max 0.08 max
N 0.03 0.03 0.03 0.03 0.03 0.03 0.03
Cr 16-18 17-19 18-20 24-26 16-18 17-19 17-19
Ni 6-8 8-10 8-12 19-22 10-14 9-12 9-13
Mo 2-4
Ti 5x %C
Nb 10x %C
Mn 1.50 1.50 1.50 1.50 1.50 1.50 1.50
Table 2.3-2: Tentative list of precipitates significant to ASS [23]

Precipitate Structure Parameters [nm] Composition
NbC fcc a = 0.447 NbC
NbN fcc a = 0.440 NbN
TiC fcc a = 0.433 TiC
TiN fcc a = 0.424 TiN
Z phase tetragonal a = 0.3037, c = 0.7391 CrNbN
M23C6 fcc a = 1.057 – 1.068 Cr16Fe5Mo2C6 (e.g.)
M6C diamond cubic a = 1.062 – 1.128 (FeCr)2 1Mo3C, Fe3Nb3C, M6S
σ phase tetragonal A = 0.880, c = 0.454 Fe – Ni – Cr – Mo
Laves phase hexagonal a = 0.473, c = 0.772 Fe2Mo, Fe2Nb
χ phase bcc a = 0.8807 – 0.8878 Fe36Cr12Mo10
G phase fcc a = 1.12 Ni16Nb6Si7, Ni16Ti6Si7
Tables Page 163

Table 3.1-1: Commercial specification and chemical composition of the samples
Element C Cr Fe Mn Mo N Ni S P Si
Commercial 0.08 16.00 balance
2.00 2.00 0.10 10.00 0.03 0.04 0.75
specification max 18.00 max 3.00 max 14.00 max max max
Samples 0.06 17.20 66.90 1.30 2.20 - 11.70 0.014 0.026 0.60
Table 3.2-1: DC carburising and nitriding treatment conditions

Gas composition
Treatment Temperature time Pressure
H2 N2 CH4
DC Nitriding 400ºC 10 h 75% 25% - 500 Pa
DC Carburising 450ºC 10 h 97% - 3% 500 Pa
Table 3.2-2: ASPC assessed treatment conditions

T = 450°C Pressure range [Pa]
t = 10 h
Gas = H2-3%CH4 30 80 125 250 400
0 • • •
5 • • • • •
Bias 10 • • •
level
[%] 15 • • • • •
20 • •
25 • •
Applied ⋅ power [ kVA]

Bias[%] = ⋅ 100
15kVA
Tables Page 164

Table 3.2-3: ASPN assessed treatment conditions
T = 400°C Pressure range [Pa]
t = 10 h
Gas = H2-25%N2 30 75 100 125 150 250
0 •
Bias level
5 •
[%]
10 • • • • •

Bias[%] = ⋅ 100
15kVA
Table 3.2-4: Active screen mechanisms: assessed treatment conditions

T = 450°C / 420°C Pressure range [Pa]
P = 400 Pa
t = 10 h DC FP ASsh ASbh
Carburising • • • •
Treatment
N2 enhanced
• • • •
carburising
Nitriding • • • •
Notation: DC - Direct Current; FP - Floating Potential; ASsh - Active Screen mesh with small holes
(Ø= 8mm); ASbh – Active Screen mesh with large holes (Ø= 25.4mm)
Table 3.3-1: Instrumented hardness settings

Variable Value
Type of experiment Depth vs. Load
Type of indentor Berkovich pyramid
Initial load 0.01 mN
Maximum load 200.00 mN
Loading rate 5 mN/s
Dwell at maximum load 5s
Displacement between indents x=25 μm, y=15 μm
Thermal drift correction Enabled
Tables Page 165

Table 3.3-2: Stylus profilometer settings for different measurements
Parameter Roughness Wear track RS bending discs
Filter Gaussian 2CR 2CR
λc 0.8 mm 2.5 mm 0.8 mm
E length / S length 5.0 mm 2.5 mm 25.0 mm
R speed = M speed 0.5 mm 0.5 mm 0.5 mm
Standard ISO / BS ANSI / JIS 82 ANSI / JIS 82
Data Ra / Ry / Rz PPFL PPFL
Tip radius 2 μm 2 μm 2 μm
Table 3.3-3: AFM settings

Tip
Height 2.5 μm - 3.5 μm
Front and side angles 35º
Tip radius 20 nm
Cantilever
Material Silicon nitride
Top layer Au (60 nm)
Shape Triangular
Length 180 μm
Width 33 μm
Elastic constant 0.12 N/m
Table 3.3-4: XRD settings

Variable Value
Scan – Detector arrangement θ - 2θ
Step size [2θ] 0.02º
Scan step time [s] 1.00 s
Scan type Continuous
Anode material Cu
Generator settings 40 kV, 40 mA
Used wavelength (Kα1) 1.540 Å
Tables Page 166

Table 3.3-5: SEM and EBSD camera settings for COM
Microscope
Acceleration Voltage 20 kV
OL Aperture 3
Probe current 110 μA (12)
Working distance 15 mm
Tilt angle 70º
Map
Crystal map size 512 pixels x 512 pixels
EBSD Camera
Acquisition mode Live
Sensitivity High
Integration time* 54 ms
Video gain* 8
Background
Average frames 10
Smooth filter size 11 x 11
Background correction Division
Solver set up
Minimum indexed bands 4
Maximum solution error 5
Depth of search for solution Optimum
Hough resolution High accuracy
Filter size 9 (Def)
Detect minimum number of bands 5
Hough radius 48
Min relative intensity 0.10
Reflective planes 37
Texture {001} <110>
* The values here reported are approximate as these parameters are sample
sensitive, and were altered in each case.
Tables Page 167

Table 3.4-1: Composition and properties of WC-Co binder bearing balls used for wear and friction tests
Composition
Tungsten Carbide 93 - 95%
Cobalt 5 - 7%
Typical properties
Hardness 90.5 - 91.5 HRA
Transverse Rupture Strength @ 20°C 2600 N/mm2
Fracture Toughness Kc @ 20°C 12 MN/m1/2
Compressive Strength @ 20°C 6200 N/mm2
Poisson’s Ratio 0.22
Magnetic Properties Slightly Magnetic
Table 3.6-1: Optronic Labs OL 730-9Q reflex telescope - Technical specifications

Variable Value
Lens type Fused silica
Focal length 203 mm
Clear aperture Φ = 60 mm
Focus (nominal) 85 cm to ∞
Field of view apertures 1.5, 3 and 5 mm
Field of view at ∞ (nominal) 0.5º, 1.0º and 1.5º
Minimum source diameter @ 85 cm 20 mm approximately
Wavelength range 250 nm - 2500 nm
Tables Page 168

Table 3.6-2: Jobin Yvon Triax 180 monochromator - Technical specifications
Variable Value
Focal length 190 mm
Entrance aperture ratio f / 3.9
Grating size 50 mm x 50 mm
Image magnification at exit 1.00
Scanning range* 0 nm - 1400 nm
Spectral dispersion* 3.53 nm / mm
Spectral resolution* 0.3 nm @ 500 nm
Wavelength positioning accuracy + / - 0.3 nm
Wavelength repeatability 0.06 nm
Wavelength drive step size* 0.06 nm
*with 1200 gr/mm grating
Table 3.6-3: Jobin Yvon Spectrum ONE detector and CCD 3000 controller unit specifications
Variable Value
Detector type CCD
Sensor array 1024 pixels x 256 pixels
Cooling method Thermoelectric (Peltier)
Operating temperature -30ºC
ADC limit 16 bit
Controller speed 166 kHz
Table 3.6-4: OES calibration conditions

Variable Value
Integration time 0.1 s
Slit width 0.013 mm
Grating 1200 gr/mm
Dark offset CCD correction Enabled
Tables Page 169

Table 4.1-1: Constants of equations (4.1-1) to (4.1-3) depending on the gas mixture
Gas mixture k1 k2 k3
3% CH4 - 97% H2 89.04 0.3182 1.45
25% N2 - 75% H2 82.22 0.3357 1.72
Table 4.1-2: ASPC layer thickness (GDOES) after treatment under different conditions
ASPC Pressure [Pa]
T = 450ºC, t = 10 h
3%CH4 – 97%H2 30 80 125 250 400
0 0.5 μm 0.5 μm 0.5 μm
5 14.0 μm 16.5 μm 2.0 μm 0.5 μm
Bias level 10 14.0 μm 17.0 μm 9.0 μm
[%] 15 14.0 μm 16.0 μm 20.0 μm 13.0 μm 0.75 μm
20 14.0 μm 16.0 μm
25 14.0 μm 18.0 μm

Bias[%] = ⋅ 100
15kVA
Table 4.1-3: ASPN layer thickness (SEM) after treatment under different conditions
ASPN Pressure [Pa]
T = 400ºC, t = 10 h
25%N2 – 75%H2 30 75 100 125 150 250
0 6.2 μm
Bias level
5 6.5 μm
[%]
10 6.6 μm 5.8 μm 5.2 μm 5.4 μm 5.0 μm

Bias[%] = ⋅ 100
15kVA
Tables Page 170

Table 4.1-4: Mean residual stresses measured from the bending of thin discs after ASPC
Layer Disc Maximum Radius of

Condition Stoney [BS] Mèzin et al Wang et al
thickness thickness Deflection curvature
P030B05 14 μm 515 μm 45 μm 1.7921 m -0.489 GPa -0.533 GPa -0.311 GPa
P125B15 20 μm 530 μm 90 μm 0.8962 m -0.725 GPa -0.815 GPa -0.485 GPa
Note: Refer to appendix C for details on these calculations
Table 4.2-1: Instrumented indentation results from AISI 316 UT and AISI 316 PC samples
Maximum depth [nm] Plastic depth [nm] Hardness [GPa] Elastic Modulus [GPa]
Sample E/H
Average Std. dev. Average Std. dev. Average Std. dev. Average Std. dev.
AISI 316 2,156.97 41.79 2,093.27 42.68 1.95 0.08 206.22 6.64 105.75
ASPC 1,030.46 23.96 881.72 23.77 10.54 0.59 215.91 11.97 20.48
Table 4.3-1: Roughness measured on Cu samples after treatment under different conditions
Ra [um] DC AS
Nitriding 0.310 μm 0.139 μm
Carburising 0.232 μm 0.187 μm
N2 enhanced carburising 0.234 μm 0.175 μm
Table 4.4-1: Assessed conditions and summary of pin-on-disc wear results
Theoretical Measured
Sample label Pressure Bias Roughness Hardness
worn volume* worn volume
AISI 316 N/A N/A 0.0801 μm 200.20 HMV0.025 3.1924 mm3 2.7130 mm3
DCPC 400 400 Pa N/A 0.0837 μm 837.37 HMV0.025 0.0075 mm3 0.0052 mm3
ASPC 125 125 Pa 15% 0.0772 μm 866.54 HMV0.025 0.0150 mm3 0.0059 mm3
ASPC 030 30 Pa 5% 0.0716 μm 857.05 HMV0.025 0.0120 mm3 0.0054 mm3
*Note: the theoretical worn volume was calculated, assuming that no significant wear of the pin took place,
using the following equation:
⎡ ⎤
( )
1
⎛ d ⎞ ⎛d ⎞
V = 2πR ⎢r 2 sin −1 ⎜ ⎟ − ⎜ ⎟ 4r 2 − d 2 2 ⎥
⎣ ⎝ 2r ⎠ ⎝ 4 ⎠ ⎦
Tables Page 171

Table 4.4-2: Composition of wear debris (EDX) for AISI 316 UT and AISI 316 PC
AISI 316 PC
Element AISI 316
(oxide layer)
C [wt%] 7.4 1.5
O [wt%] 39.2 43.0
Cr [wt%] 9.7 10.0
Mn [wt%] 0.9 0.8
Fe [wt%] 35.8 34.0
Co [wt%] 0.4 0.2
Ni [wt%] 5.7 6.2
Mo [wt%] 0.7 0.6
W [wt%] 0.2 3.7
Table 4.4-3: Summary of results obtained on the wear debris

Wear debris Colour Size Magnetic Possible phases
AISI 316 PC Red / Orange < 20 μm No α-Fe2O3 Haematite
Fe3O4 Magnetite
AISI 316 UT Black > 20 μm Yes
C0.05Fe1.95 Martensite
Table 4.4-4: Summary of friction results

Hardness Roughness Average coefficient of friction
Disc
[HMV0.05] Ra [μm] AISI 316 ball WC-Co ball ASPC ball
AISI 316 UT 311.3 0.292 0.61 0.40 0.55
ASPC 837.7 0.278 1.06 0.63 0.80
Tables Page 172

Table 4.5-1: Corrosion factor for corrosion tests in boiling 16% H2SO4 with CuSO4 for 20 hours
Samples Corrosion factor*
DCPC 400 5.14
ASPC 125 4.29
ASPC 030 3.67
*Note: the corrosion factor was calculated according to the following equation:
ΔM treated
CF =
ΔM AISI 316
Table 5.1-1: Electric parameters in DC and AS furnaces under similar discharge conditions
Furnace Pressure Current Voltage Power
DC 400 Pa 5.0 A 550 V 2.75 kVA
AS 150 Pa 6.0 A 540 V 3.24 kVA
DC 125 Pa 2.0 A 800 V 1.60 kVA
AS 50 Pa 2.2 A 896 V 1.97 kVA
Table 5.2-1: Carbon diffusivity calculated from different treatment conditions
Treatment Carbon diffusivity K

450ºC – 3%CH4 [cm2 / s]
DCPC 1.11 · 10-10
ASPC P125B15 1.11 · 10-10
ASPC P030B05 5.44 · 10-11
x = a(Dt )
1/ 2
= Kt 1 / 2
Tables Page 173

Table 5.2-2: Lattice expansion measured on EA from the XRD peak shift
hkl EA lattice expansion
111 2.34%
200 3.32%
220 2.53%
311 3.02%
222 2.61%
Table 5.2-3: Parameters used for estimation of residual stresses from the instrumented indentation test
Variable Symbol Value
Maximum applied load P1 200 mN
Load at intersection point B P2 40 mN
Experimental constant α 65.3º
Depth of residual indentation h 750 nm
*Note: Refer to figure 5.2-12 for details on the variables
Table 5.5-1: Bond enthalpies [kJ / mol] [340]

H C N O
H 436
C 412 348 (i)
612 (ii)
518 (a)
N 388 305 (i) 163 (i)
613 (ii) 409 (ii)
890 (iii) 945 (iii)
O 463 360 (i) 146 (i)
743 (ii) 497 (ii)
Reference: (i) single bond, (ii) double bond, (iii) triple bond, (a) aromatic
Tables Page 174

FIGURES AND ILLUSTRATIONS
Figure 2.1.1-1: Historical evolution of materials and their relative importance [1]
Figure 2.1.1-2: Young’s modulus - Strength materials selection chart [1]
Figures and illustrations Page 175

Figure 2.1.1-3: Fracture toughness – Young’s modulus materials selection chart [1]
Figure 2.1.1-4: Strength - Density materials selection chart [1]

Figure 2.1.1-5: Strength - Relative cost materials selection chart [1]

Figure 2.1.1-6: Corrosion resistance materials selection chart [1]

A = austenite; M = martensite; δF = delta ferrite
Figure 2.1.2-1: Schaeffler diagram for stainless steel classification [5]
Figure 2.1.3-1: Fe-Cr-Ni ternary phase diagram [13]

Figure 2.1.3-2: Schematics of Ms and Md for martensitic transformation in ASS [18]
Figure 2.1.3-3: Stress induced martensitic transformation of ASS at different temperatures [16]

Figure 2.1.3-4: Solubility of carbon in austenitic stainless steel 18/8 [37]
Figure 2.1.3-5: Reference carbide precipitation sequence [22]

550˚C
Phase / Precipitation site Precipitation / Dissolution
600˚C
Laves phase intergranular
Laves phase at grain boundaries
Sigma phase at grain boundaries
Sigma and Laves phases in ferrite
M23C6 carbides at grain boundaries
10 h 100 h 1000 h 10,000 h 100,000 h
Figure 2.1.3-6: Ageing times for phase precipitation in AISI 316 at 550ºC and 600ºC [26]
Figure 2.1.4-1: Schematics of polarisation curve of ASS in sulphuric acid [38]

Figure 2.1.4-2: Effect of alloying elements on the polarisation curve of ASS [38]
Figure 2.1.4-3: Metallurgical features detrimental to the corrosion resistance of ASS [38]

Figure 2.1.5-1: Wear resistance materials selection chart [1]
Figure 2.1.5-2: Wear rate transitions [55]

Normal load
Interacting asperities
Sliding direction
Normal load
Transferred material
Sliding direction
Figure 2.1.5-3: Transfer of material between interacting asperities and deformation of the
subsurface
Figure 2.2.1-1: Schematic of the stress and mechanical strength diagram for a cross section of
a surface engineered component between the neutral axis and the surface [88]

Figure 2.2.1-2: Typical thickness obtained with surface engineering processes [81]
Figure 2.2.1-3: Energy content vs strength chart for different materials [1]

Figure 2.2.2-1: Schematic representation of the reaction steps in gas carburising [94]

Figure 2.2.3-1: Metal-metal oxide equilibrium curves in hydrogen atmospheres [151]

Figure 2.2.3-2: Threshold Temperature-time curves to produce precipitation free
microstructures upon plasma nitriding (PN) and plasma carburising (PC) on AISI 316 [105]
Figure 2.2.3-3: GDOES composition depth profile of AISI 316 plasma carburised and nitrided

DARK DISCHARGE GLOW DISCHARGE ARC
Townsend regime
Breakdown voltage
VB Corona E
Glow to arc transition
Potential, U [V]
D H
High intensity
I arcs
C
Saturation G
regime F' F
B K
A Low intensity J
Normal glow Abnormal glow arcs
Background ionisation
10 -10 10 -8 10 -6 10 -4 10 -2 1 100 1,000

Current, I [A]
Figure 2.2.5-1: Current - voltage characteristic curve for DC plasma [157]
DCPC ASPC
Vessel Vessel
Active Screen
Worktable Worktable
Bias
Earth power supply Earth
Main power
supply
Main power
supply
Figure 2.2.6-1: DC and AS furnaces for plasma carburising (DCPC and ASPC)

Figure 2.3.1-1: Maxwell electron energy distribution function – up: most probable velocity, ū:
average velocity, ueff: r.m.s. velocity [189]
Figure 2.3.1-2: Typical Pashen curve [224]

Figure 2.3.3-1: Structure of the glow discharge [157]

Figure 2.3.4-1: Diagram of electronic, vibrational and rotational energy levels of a molecule
[204]
Figure 2.3.4-2: Typical OES equipment [205]

Figure 2.3.4-3: Typical electric probes – (a) plane, (b) cylindrical, (c) spherical [212]
Figure 2.3.4-4: typical current voltage curve obtained with an electric probe [157]

Figure 2.3.4-5: Ion flux probe [215]
Figure 3.1.3-1: Schematics of corrosion samples

(a) (b)
Figure 3.2.1-1: (a) Klöckner Ionon DC furnace and (b) Plasma Metal active screen industrial unit
(a) DC arrangement (b) AS arrangement

at floating potential (c) Floating potential
Chamber (+) Chamber (+) Chamber (+)
Active screen (-)
Cathodic (-) Floating Floating
Main work table (-) Main work table (-) Main work table (-)
Figure 3.2.1-2: (a) DC, (b) AS and (c) FP arrangements inside a conventional DC plasma furnace
used to study the mechanisms of active screen plasma treatments.

ASsh ASbh
AS
DC
FP
DC
Figure 3.2.1-3: DC, ASsh, ASbh, and FP arrangements inside a conventional DC plasma furnace
used to study the mechanisms of active screen plasma treatments.
DC: direct current; AS: active screen; FP: floating potential; ASsh: AS mesh with small holes (Ø = 8 mm),
ASbh: AS mesh with large holes (Ø = 25.4 mm)
Figure 3.2.1-4: Fish bone diagram of the treatment conditions involved

Horizontal rotation axis
Friction force measuring axis
Pin holder
Vertical rotation axis
Applied load
Friction disc sample

Couterpart ball
Sample rotation axis
Figure 3.4-1: Schematics of the pin-on-disc apparatus used for wear and friction tests
Coil condenser
Cooling water inlet
Clamp
Cylindrical flask
Boiling acid solution

Sample holder
Cylindrical corrosion sample

Hot plate
Figure 3.5-1: Schematics of the apparatus used for immersion corrosion in boiling acid solutions

Figure 3.6-1: Experimental arrangement used for OES (telescope) and IOES (optical fibre probe)
DC arrangement AS arrangement
Chamber (+) Chamber (+)
Active screen (-)
Probe Probe
Work table (-) Work table (-)
Figure 3.6-2: DC and AS experimental arrangements used for IFP measurements

Figure 4.1-1: ASPC processing conditions on the work table
Figure 4.1-2: ASPN processing conditions on the work table

hollow cathode arcing
edge
Figure 4.1-3: Samples in a DC conventional treatment, showing arcing on a dirty or rusty

specimen, and hollow cathode effect on a sample with a blind hole.
An Active Screen experimental arrangement is also seen on the left side of the same picture.
DC DC DC
arcing edge effect hollow cathode

AS AS AS
Figure 4.1-4: Surface damage by process instabilities in DC conventional treatments

Figure 4.1-5: Layer thickness (size of the bubble) superimposed on the map of treatment conditions
for ASPC and ASPN
Figure 4.1-6: Typical profile of the thin discs used for the assessment of residual stresses

AISI 316 Untreated AISI 316 plasma carburised
Figure 4.2-1: Optical micrographs of the same area before and after plasma carburising
AISI 316 Untreated AISI 316 plasma carburised
Figure 4.2-2: EBSD Crystal Orientation Maps of the same area before and after plasma
carburising
Figure 4.2-3: GDOES composition-depth profiles for different treatment times:

(A) 1 hour, (B) 3 hours and (C) 6 hours

Figure 4.2-4: Typical cross section micrograph of an AISI 316 plasma carburised specimen
DCPC ASPC
Figure 4.2-5: SEM micrographs of DCPC and ASPC treated samples
Figure 4.2-6: AFM images of DCPC and ASPC treated samples

Oxide layer
Oxide layer
Figure 4.2-7: TEM micrograph and diffraction pattern (amorphous) of the oxide layer on DCPC
and ASPC samples (top view)
Figure 4.2-8: TEM micrograph and ring electron diffraction pattern on a plasma carburised specimen

Figure 4.2-9: Electron diffraction pattern of the carbon expanded austenite on a plasma
carburised specimen
Figure 4.2-10: XRD pattern obtained on DCPC and ASPC, and austenite reference pattern

Extrapolation function cosθ.cotθ
Figure 4.2-11: Lattice parameter ahkl vs cosθ.cotθ of expanded austenite and AISI 316 UT
Figure 4.2-12: GDOES composition-depth profile of DCPC and ASPC treated samples

Figure 4.2-13: Load bearing capacity (LBC) of DCPC and ASPC treated samples
Figure 4.2-14: Cracks inside a low-force (500g) Vickers indentation on a DCPC sample

Figure 4.2-15: Instrumented hardness on AISI 316 untreated and ASPC treated samples
Figure 4.3-1: Appearance of the samples treated under DC and AS arrangements in nitriding,
carburising and nitrogen enhanced carburising atmospheres

Figure 4.3-2: XRD patterns of AISI 316 treated under DC and AS arrangements in nitriding, carburising and N2 enhanced carburising atmospheres

Figure 4.3-3: GDOES composition-depth profiles of samples treated under DC and AS
arrangements in nitriding, carburising and N2 enhanced carburising atmospheres

Figure 4.3-4: Load bearing capacity (LBC) of samples treated under DC and AS arrangements
in nitriding, carburising and N2 enhanced carburising atmospheres

Figure 4.3-5: Optical micrograph of a hardness indent on one AISI316 sample after ASPN
Figure 4.3-6: Vickers microhardness tests on different parts of the AISI304 stripe specimens
treated in an AS arrangement with big holes in the mesh
AS: Active screen, PN: plasma nitriding, PC: plasma carburising, PCN: nitrogen enhanced carburising, H: hole area

ASPN ASPC ASPCN
Figure 4.3-7: Optical micrographs of the deposition layer on ASPN, ASPC and ASPCN copper
samples
ASPN ASPN
ASPC ASPC
ASPCN ASPCN
Figure 4.3-8: Morphology of AS nitrided, carburised and N2 enhanced carburised samples observed under
SEM and AFM

Figure 4.3-9: XRD patterns of copper samples treated under DC and AS arrangements in nitriding, carburising and N2 enhanced carburising atmospheres

ASPC ASPN
Figure 4.3-10: ASPC and ASPN treated glass slides
Figure 4.3-11: XRD peaks of the deposition layer on ASPN treated glass slides

AISI 304 mesh for AS
experiments inside
the DC furnace
Figure 4.3-12: Micrograph and EDX spectrum of the mesh material used in the AS experimental
settings inside DC furnaces.
Low carbon steel

mesh installed in
the AS furnace
Figure 4.3-13: Micrograph and EDX spectrum of the mesh material used in the AS industrial unit

AISI 316 UT AISI 316 PC
Figure 4.4-1: Typical appearance of the wear tracks on AISI 316 UT and AISI 316 PC
Figure 4.4-2: Appearance of the WC-Co ball worn against AISI 316 UT and AISI 316 PC
Figure 4.4-3: Measured worn volume after pin-on-disc test

Figure 4.4-4: SEM images of the wear tracks on AISI 316 UT and AISI 316 PC
Cr Fe
Ni O W

WC-Co vs AISI 316 UT WC-Co vs AISI 316 PC
Figure 4.4-7: SEM images of the wear scars of WC-Co balls worn against AISI 316 UT and
AISI 316 PC
WC-Co vs AISI 316 UT WC-Co vs AISI 316 PC
Figure 4.4-8: SEM images of the material accumulated at the trailing edge of the wear scar of
WC-Co balls worn against AISI 316 UT and AISI 316 PC

Cr Fe
O W Co
Figure 4.4-9: EDX mapping of the wear scar left on the WC-Co ball worn AISI 316 UT
Fe O
Figure 4.4-10: EDX map of the wear scar left on the WC-Co ball worn against AISI 316 PC
Figure 4.4-11: Wear debris from untreated and carburised AISI 316 respectively

Figure 4.4-12: SEM BSE micrograph of wear debris from AISI 316 UT and AISI 316 PC
Figure 4.4-13: Electron diffraction patterns on wear debris from AISI 316 UT and AISI 316 PC
Figure 4.4-14: TEM micrograph of wear debris from AISI 316 PC and the EDX spectrum

Figure 4.4-15: XRD pattern of the deformed material on the wear track of AISI 316 UT
Figure 4.4-16: Hardness profile measured on the cross section of one AISI 316 UT sample
worn against WC-Co

Sliding direction
Figure 4.4-17: SEM cross section image of the wear track of AISI 316 UT worn against WC-Co
Crystal orientation Misorientation Phase map - martensite
Figure 4.4-18: EBSD crystal orientation maps of the distorted layer, and martensite phase map on
the cross section of the wear track of one AISI 316 UT specimen
The arrow indicates the sliding direction
Cross section on treated layer

Cross section on wear track
Figure 4.4-19: EBSD crystal orientation maps on cross sections of an AISI 316 PC specimen
The arrow indicates the sliding direction

Figure 4.4-20: Coefficients of friction obtained from different material pairs

AISI 316 UT AISI 316 ASPC
Figure 4.5-1: Immersion corrosion test in H2SO4 16% solution at room temperature for 120 h
AISI 316 – Attack on a MnS inclusion; ASPC – Deposition layer of carbides pealing off
AISI 316 DCPC 400
ASPC 125 ASPC 030
Figure 4.5-2: Surface appearance of AISI 316, DCPC 400 , ASPC 125 and ASPC 030
specimens corroded in boiling H2SO4 16% solution
Figure 4.5-3: Cross section of AISI 316 UT and PC specimens exposed to boiling H2SO4 16%
solution for 1 hour

Figure 4.5-4: Cross section of a PC specimen exposed to boiling H2SO4 16% solution for 1 h
Localised attack on MnS inclusions
Figure 4.5-5: Cross section of a PC specimen corroded in boiling H2SO4 16% solution for 1 h
Localised attack on slip bands

Figure 4.5-6: Plan view of a PC specimen immersed in boiling H2SO4 16% solution for 15 h
Localised attack on grain boundaries
Figure 4.5-7: Cross section of a PC specimen corroded in boiling H2SO4 16% solution for 1 h
Corrosion progressing through grain boundaries of the AISI316 substrate once the EA layer
had been penetrated

Untested
AISI 316
DCPC400
ASPC125
ASPC030
Figure 4.5-8: Rod samples used for corrosion tests in boiling H2SO4 16% solution
Figure 4.5-9: Mass loss specimens after immersion corrosion test in boiling H2SO4 16%
solution for 20 hours

AISI 316 DCPC 400
ASPC 125 ASPC 030
Figure 4.5-10: Coupon samples exposed to boiling H2SO4 16% solution with CuSO4 for 20 h
Figure 4.5-11: Optical micrographs of specimens corroded in boiling H2SO4 16% solution with
CuSO4 for 20 h
Figure 4.5-12: SEM micrograph of pits coalescing at the intersection of slip bands with a grain
boundary, and AFM image of the attack on slip bands and formation of ditch grain boundary

EDX line scan
for carbon
Figure 4.5-13: SEM micrograph of a ditch type grain boundary and EDX Carbon line scan on a
similar boundary
Figure 4.5-14: SEM micrographs of samples corroded in boiling HNO3 20% solution for 240 hours

Figure 4.5-15: AFM image of localised corrosion at grain boundaries and cross section data.
Sample DCPC 400 after immersion corrosion test in boiling HNO3 20% solution for 240 hours
Figure 4.5-16: Localised attack on samples exposed to boiling HNO3 20% solution for 240 h
Figure 4.5-17: Corrosion rates in boiling HNO3 20% solution for different periods of time

Carburising Nitrogen enhanced carburising Nitriding
Figure 4.6-1: Low and high resolution spectra Figure 4.6-2: Low and high resolution spectra for Figure 4.6-3: Low and high resolution spectra for
for plasma carburising nitrogen enhanced plasma carburising plasma nitriding

Figure 4.6-4: Simplified emission intensity map obtained for ASPN
Figure 4.6-5: Summary of the OES intensity maps obtained under ASPC and ASPN treatment
conditions

Figure 4.6-6: Correlation between OES emission intensity and the electric parameters of the furnace under ASPC and ASPN treatment
conditions

Figure 4.7-1: Oscillations in the floating potential measured with the IFP under DC and AS
arrangements inside a DC furnace.
Figure 4.7-2: Floating potential and ion flux measured under DC and AS experimental
arrangements inside a DC furnace, in carburising and nitriding gas mixtures
Figure 4.7.3: Oscillations observed in the FP of the IFP inside the AS industrial unit

Figure 4.7-4: Average FP measured with the IFP under different ASPC and ASPN conditions
Figure 4.7-5: IFP drain curves obtained at floating potential in ASPC and ASPN conditions
Figure 4.7-6: Ion flux calculated from the drain curves of the IFP in ASPC and ASPN conditions

Figure 5.1-1: I-V electric curves obtained for ASPC and ASPN at different gas pressures
Figure 5.1-2: Bias set point and real bias power applied for ASPC and ASPN conditions
Figure 5.1-3: Bias current vs bias set point for ASPC and ASPN

Figure 5.1-4: Worktable power for different ASPC and ASPN treatment conditions (bias levels and
pressures)
Figure 5.1-5: Characteristic I-V curves for ASPC and ASPN with E/p as bubble size

Figure 5.2.1: Layer thickness vs treatment time
Figure 5.2-2: EBSD pattern quality vs carbon concentration at plateau (GDOES carbon profile)

Figure 5.2-3: Optical micrograph on a plasma carburised specimen
Figure 5.2-4: XRD pole figures obtained on AISI 316 UT and AISI 316 PC

Figure 5.2-5: AFM image of a grain with activated crossed slip systems and cross section profiles
Figure 5.2-6: AFM plane view of PC samples and crystal mimic obtained from EBSD COMs

AISI 316 PC
AISI 316 UT
Figure 5.2-7: Misorientation measured by EBSD on the same area of the sample before and after
plasma carburising
Figure 5.2-8: EBSD crystal orientation (normal direction) before and after PC respectively
Figure 5.2-9: CSL Σ3 grain boundaries before and after PC respectively

Figure 5.2-10: Distribution of residual stress: average, triangular, GDOES and strain hardened
profiles
Figure 5.2-11: Hardness profiles calculated from LBC and Knoop hardness profile
Figure 5.2-12: Estimation of residual stresses from instrumented indentation tests according to
[238]

Figure 5.3.1-1: SE image of the cross section of a wear track on AISI 316 UT with EBSD COM
superimposed and inverse pole figure obtained from that same area of the sample
Figure 5.3.1-2: Signs of accumulated plastic strain (3 steps of deformation) at the edge of the
wear track of AISI 316 UT, and schematics of the deformation in the subsurface region.

Figure 5.3.2-1: Failure of the layer of carbides at the edge of a wear track on AISI 316 PC
Figure 5.3.2-2: Smooth surface of the underlying EA layer, and protective oxide layer formed
during sliding wear

1 2
3 4
Figure 5.3.2-3: Genesis of the protective oxide layer on a PC specimen
Figure 5.3.2-4: Detachment of WC particles from the counterpart ball

Figure 5.3.2-5: Morphology of the protective oxide layer on a PC specimen under AFM
Figure 5.3.2-6: Crack propagation along the original deformation morphology in the protective
oxide layer

2- Propagation of cracks 3- Propagation and
parallel to the sliding intersection of cracks 4- Detachment of wear
1- Nucleation of cracks direction (cutting action of debris particles
perpendicular to the sliding asperities and residual
direction stresses)
Figure 5.3.2-7: Process of detachment of wear debris from the protective oxide layer. SEM
image and schematics
Figure 5.3.2-8: Cracks on a thick portion of the protective oxide layer

Figure 5.4.1-1: Corrosion potential of ASS in different acid solutions vs saturated calomel
electrode [2]
Element Weight %
C 19.1
O 7.7
S 0.3
Cr 17.0
Mn 1.2
Fe 48.0
Ni 1.4
Cu 3.1
Mo 2.2
Figure 5.4.2-1: SEM micrograph and chemical composition according to EDX of material pealed
off from a PC sample at early stages of a corrosion test in boiling sulphuric acid
Figure 5.4.2-2: XPS spectrum obtained from the surface of an ASPC sample

Figure 5.4.3-1: Schematics of the corrosion mechanisms observed on carbon expanded austenite

Figure 5.4.3-2: Morphology of specimens corroded in boiling H2SO4 16% solution with CuSO4
AISI 316 UT AISI 316 UT AISI 316 UT
AISI 316 PC AISI 316 PC AISI 316 PC
Figure 5.4.4-1: Inverse pole figures obtained by EBSD on the same area of the sample before
and after PC

Σ number
Figure 5.4.4-2: Fraction number of special grain boundaries before and after PC
Figure 5.4.4-3: Edge effect revealed by microhardness measurements across the surface of a
DCPC sample

Figure 5.5.2-1: Optical emission spectra collected at different gas pressures in a 75% N2 - 25% H2
gas mixture
ASPN 30 Pa - 0% Bias ASPN 125 Pa - 10% Bias
Figure 5.7.1-1: Morphology of the deposition layer under different ASPN treatment conditions
Figure 5.7.1-2: Deposition layer on grains with different crystallographic orientations

Figure 5.7.1-3: Sputtering and redeposition model for DC [154] and AS plasma nitriding
SEM image Fe
Cr Ni
Figure 5.7.1-4: Deposition layer on a glass slide treated in an AS arrangement with an AISI 304
mesh

Figure 5.7.1-5: Deposition layer (EDX) vs expanded austenite layer thickness (GDOES)
Figure 5.7.1-6: Detachment of the deposition layer of iron nitrides AS plasma nitrided at floating
potential

Figure 5.7.2-1: TEM micrograph of the deposited particles and EDP
Figure 5.7.2-2: SEM micrograph and XRD pattern from carbide film deposited on the walls of
the AS furnace

Appendix A: OES optical fibre probe construction details
The spectra collected with the telescope were useful to identify the active species present in the plasma,
although no clear trend could be found when comparing the emission intensities at different treatment
conditions. This can be explained considering that the mesh of the active screen furnace is designed to
form hollow cathodes in different ways, depending on the treatment conditions. The existence of hollow
cathodes in the field of view could not be avoided nor kept constant, and the emission intensity was
significantly affected by them. Furthermore, it did not represent the conditions on the work table.
Therefore, collection of light from the worktable, in the proximity of the samples or components was
considered of interest.
Aomolin Ltd UV-Vis silica optical fibre of core diameter 100/110 μm (NA 0.22) was selected for the
construction of the probe. The fibre was cut into 5 m long strings, and four strings were threaded
together through the stainless steel shell. A bundle of four optical fibres was necessary in order to
increase the intensity of the signal, which was otherwise too weak, especially when the high resolution
grating was used, i.e. with larger spectral dispersion. This method was good enough for the purpose of
the current work, although alignment was problematic, and probes made with single fibres of larger core
diameter could be useful for future applications.
The shell of the feedthrough was made of a stainless steel tube, with a quick fit type flange on one end,
which allowed an easy attachment to any of the standard instrumentation ports of the furnace (figure
A.1). An insulating and temperature resistant ceramic adhesive, Aremco Ceramcast 586 (ZrSiO4), was
used to fill the gap between the optical fibres and the stainless steel tube, and the feedthrough was
cured in an oven following the thermal cycle suggested by the supplier (table A-1). Finally, the outer side
of the feed through was sealed with an epoxy resin to reduce the leaks and not to affect the quality of
the vacuum in the furnace.
The optical fibre feedthrough was then installed in the active screen furnace and the fibres were placed
on top of ceramic insulators. It is worth noting that if the optical fibres are subjected to the cathodic
potential of the work table during the treatment, severe arcing takes place, with the associated instability
of the process and risk of permanent damage or destruction of the optical fibres.
The polymeric buffer coating of the fibres did not resist the operating conditions, but a layer of metallic
material was deposited on the fibres after only a few hours of exposure to the plasma. This metallic
Appendix A Page 258

coating was found to protect the fibres, making them tougher, and also contributed to block stray light
from other parts of the plasma volume inside the furnace. Therefore, light was only collected from a
small area in front of the open end of the fibres, achieving a spatial resolution much higher than with the
telescope.
An insulating ceramic tube was used to aim the bundle of fibres in the direction of interest and to reduce
deposition of sputtered material on their open ends. Nonetheless, deposition still blocked the fibres after
several hours of exposure to the plasma and, as a result, it was necessary to cleave the fibres before
each experiment, and to shorten the data collection time as much as possible in order to get intense and
comparable signals.
The other ends of the optical fibres were stripped from the buffer polymer coating, cleaved and fitted
with an SMA connector, to feed the signal into the Triax 180 spectrometer.
For the assessment of the transmission efficiency before and after exposure to the plasma environment,
their respective transmission efficiencies, in the range 200 nm to 1100 nm, were recorded and
compared. The exposed and unexposed optical fibres were fitted with Bullet bare fibre connectors and
plugged into an Ocean Optics HL-2000-FHSA halogen light source (table A-2) and an Ocean Optics
HR2000 high resolution miniature fibre optics spectrometer (table A-3).
Analysis of potential sources of error [1]

In order to confirm the validity of the collected signal, some of the probable sources of error were
assessed. In first place, the effect of the plasma on the transmission efficiency of the optical fibres was
considered. A deposition layer of, mainly, iron nitride covered a large proportion of the surface of the
optical fibres exposed to the plasma (figure A-2), and the effect of this layer of material on the
transmission efficiency was uncertain. Therefore, the transmission spectra of optical fibres exposed and
unexposed to the plasma were compared. No significant difference was observed between the two
transmission spectra (figure A-3), which indicated that the fibres were in good condition even after
several tens of hours exposed to the N2 - H2 and CH4 - H2 plasma atmospheres.
In addition, the deposition layer was found to coat the open end of the optical fibres after only a few
hours of exposure to the plasma, and this coating hindered light from being collected. For this reason,
Appendix A Page 259

the fibres had to be cleaved before each set of measurements. However, the cleavage mode of the
fibres was of importance: whilst a clean cut perpendicular to the longitudinal axis produced the highest
collection efficiency, a rough end significantly reduced the collected signal. Consequently, the cleavage
mode was studied, and it was found that the optical fibres exposed to plasma were most frequently
cleaved at 90º from their longitudinal axis (figure A-4). Furthermore, a poor condition of the open ends of
the fibres could be identified and avoided before the experiment.
[mm]
Figure A-1: Dimensions of the stainless steel shell for optical fibre feedthroughs
Figure A-2: Deposition layer observed on an optical fibre exposed to the plasma in an AS
furnace
Appendix A Page 260

Figure A-3: Transmission spectra of optical fibres exposed and unexposed to the plasma
Figure A-4: Cleavage mode of optical fibres exposed to the plasma
Table A-1: Aremco Ceramcast 586 curing cycle

Type Temperature Time
Air Room 8 hours (minimum)
Oven 200ºF (90ºC) 2 to 4 hours
Oven 250ºF (120ºC) 3 hours
Appendix A Page 261

Table A-2: Ocean Optics Halogen light source HL-2000-FHSA – Technical specifications
Variable Value
HL-2000-FHSA Includes filter holder, attenuator and shutter
Output 7 watts
Output to bulb 1.4 A @ 5 VDC
Wavelength range 360 nm-2 µm
Stability 0.5%
Drift <0.3% per hour
Time to stabilise ~5 minutes
Bulb colour temperature 2,960 K
Table A-3: Ocean Optics HR2000 high resolution fibre optic spectrometer - Technical specifications
Variable Value
Detector Sony ILX511 linear CCD array
Detector Range 200 nm -1100 nm
Pixel size 14 µm x 200 µm
Optical bench f/4, 101 mm focal length
Gratings Choose from 13 different gratings
Pixel elements 2048
Entrance Aperture 5, 10, 25, 50, 100 or 200 µm wide slits or fibre (no slit)
Order-sorting filters Installed longpass and bandpass filters
Stray Light <0.05% at 600 nm; <0.10% at 435 nm
Dynamic Range 2 x 108 (system); 2000:1 for a single scan
Fibre Optic Connector SMA 905 to single-strand optical fibre 0.22 NA)
Data Transfer Rate Full scans into memory every 13 ms
Integration Time 3 ms to 65 s
Appendix A Page 262

Appendix B: Ion Flux Probe (IFP) construction details
OES is a very useful technique to provide information on the active species involved in the plasma.
However, the information it yields is incomplete as it comes only from excited species, while no direct
evidence is obtained from the electrons, which are the primary agents in the plasma. This kind of
information can be obtained from electric probes, and it was thus the intention in this project to develop
and use an electric probe as a complementary method for the OES plasma diagnostic technique.
A planar electric probe was made of copper, with a central disc as the actual probe and two guarding
rings surrounding it (figure B-1). The guarding rings were meant to avoid edging effects on the central
disc, making the sheath in front of it flat and even. The surface area of the central disc and the inner
guarding ring are the same, while the exposed area of the outer guarding ring is twice as large (figure B-
2). They were finely turned and the active surfaces were wet ground with silicon carbide grinding paper,
and polished with activated colloidal silica.
The isolation between the central disc and the guarding rings was achieved using DuPont Nomex
Aramid paper type 410 (table B-1). This type of temperature resistant insulating paper was found
convenient in view of its thermal resistance, dielectric and mechanical properties and low cost. From two
to four layers of 0.25 mm thick insulating paper were used in all cases and new insulating sheets and
washers were used for each experiment. The paper was found to resist the treatment conditions here
studied, but its use is not recommended for longer periods of time or higher temperatures.
The central disc was silver soldered to a copper wire and connected with the measuring circuit, through
a standard electric feedthrough, by means of gold coated pin connectors (figure B-3). The guarding
rings were not connected to the measuring circuit due to a technical inconvenient, and remained at
floating potential during the experiments.
The probe was mounted on ceramic insulating tubes, to support it and insulate it from the high cathodic
potential of the work table (up to 900 V DC). Two ceramic tubes were attached together by means of
steel bolts, which also played the role of spacers for copper wires to be connected to the probe (figure
B-1). To avoid deposition of conductive material on the live parts of the measuring circuit, the copper
wire was insulated with ceramic beads throughout its length, and it was also guided inside an insulating
Appendix B Page 263

ceramic tube until the proximity of the probe. All the ceramic insulating tubes had to be wet ground and
washed before each experiment to eliminate the layer of conductive material deposited on them.
Regarding the measuring circuit, tantalum capacitors were selected in view of their low electric charge
leak rate in air, allowing retention of charge for longer times. The 63 V and 4.7 μF tantalum capacitors
were connected to a 60 V DC power supply with a 10 Ω resistor in series. Heavy duty toggle switches
were used for the connection and disconnection of the probe and the power supply. Finally, high speed
0.8 A fuses were used to protect the measuring circuit in case of electric fault, and the operating panel
was conveniently earthed.
A low noise Instek GPS-6010 DC power supply with variable output voltage (0 V to 60 V) was
connected to charge the capacitors and, subsequently, to bias the probe (table B-2). A Pico 2202 digital
oscilloscope and 250 MHz oscilloscope probe, with an impedance of 50 MΩ and an attenuation power
of 10, were used to acquire the drain curve of the tantalum capacitors (table B-3). The oscilloscope was
connected to the USB port of a PC and the signal was monitored and stored in the hard drive of a PC
using PicoScope 5.15.6 (32 bit) data collection software.
Probe
Insulating paper
Inner guarding ring
Ceramic insulator Insulating paper
Detail A Outer guarding ring

Spacer
Probe wire
Ceramic insulator Ceramic insulator
Work table
Detail A
Figure B-1: Schematics and constructive details of the IFP
Appendix B Page 264

Central disc Inner guarding ring Outer guarding disc
Ø35.8
Ø25.6 Ø40
Ø25
Ø36.4
4.3
Ø5.6
2
4
27
19
2.3
6.1
12.1
Ø20
Ø5 Ø19.4 Ø30
[mm]
Figure B-2: IFP - Dimensions of the central disc, inner and outer guarding rings
A B C D E F G
0.93 1.57 1.57 0.53 0.43 0.032 0.25 [in]
23.6 39.9 39.9 13.5 11.0 0.81 6.3 [mm]
Figure B-3: Lesker EFT0043038A feedthrough – Stainless steel KF25 flange, 4 copper pins
Table B-1: DuPont Nomex Aramid Insulation paper type 410 – Technical specifications
Variable Value
Nominal thickness 0.25 mm
Dielectric strength (AC rapid raise) 32 kV/mm
Dielectric Strength (full wave impulse) 63 kV/mm
Dielectric constant at 60 Hz 2.7
Dissipation factor at 60 Hz 6
Appendix B Page 265

Table B-2: Instek GPS-6010 DC power supply – Technical specifications
Constant Voltage Operation
Line Regulation 0.01% +3 mV
0.01% +3 mV (rating current 3 A)
Load Regulation
0.01% +5 mV (rating current >3 A)
0.5 mVrms 5 Hz ~ 1 MHz (rating current 3 A)
Ripple and Noise
1 mVrms 5 Hz ~ 1 MHz (rating current >3 A)
Recovery Time 100 µs (50% load change, minimum load 0.5 A)
Output Range GPS-6010: 0 V to 60 V, continuously adjustable
Constant Current Operation
Line Regulation 0.2% +3 mA
Load Regulation 0.2% +3 mA
Ripple Current 3 mArms
GPS-6010: 0 A to 1 A, continuously adjustable
Output Range
(HI/LO range switchable)
Meter
Analogue voltmeter and analogue ammeter
Meter Type
2.5 class
Insulation
Chassis and Terminal 20 MW or above (500 V DC)
Table B-3: Pico 2202 digital oscilloscope – Technical specifications

Vertical selection (signal axis)
Bandwidth 5 MHz
Channels 2
Resolution 8 bits
Enhanced resolution 12 bits
Dynamic range 48 dB
Accuracy 3%
±50 mV, ±100 mV, ±200 mV, ±500 mV,
Input ranges
±1 V, ±2 V, ±5 V, ±10 V, ±20 V
Input characteristics 1 MΩ 20 pF
Overload protection ±100 V on single output
Input type Single ended BNC connector
Input coupling AC or DC (software controlled)
Horizontal selection (time axis)
Sampling rate 40 MS/s (1 GS/s ETS)
Record length 8,000 samples
500 ns, 1 μs, 2 μs, 5 μs… up to
Time ranges
50 s, 100 s, 200 s per division
Time base accuracy 0.0001 with 3 ps jitter
Appendix B Page 266

Appendix C: Residual stresses formulas
Stoney’s formula according to British Standard DD 1071-11:2005 [2]:
1 E S d S2 1
σ0 = − (C.1)
6 1 − ν S δ EA R
where σ0 is the mean value of residual stress through the thickness of the layer, ES is the elastic
modulus of the substrate, νS is Poisson’s ratio of the substrate, dS and δEA are the thickness of the
substrate and the layer of expanded austenite respectively, and R is the radius of curvature of the disc
measured after the treatment (figure C-1).
Modified Stoney’s formula proposed by A. Mézin [3]:
1 E S d S2 1 ⎡ ⎛ E EA (1 − ν S ) ⎞ δ EA ⎤
σ0 = − ⎢1 + ⎜ 4 − 1⎟ ⎥ (C.2)
6 (1 − ν S ) δ EA R ⎣ ⎜⎝ E S (1 − ν EA ) ⎟⎠ d S ⎦
where the first part of this formula is equivalent to the Stoney’s formula described above, and the term
between brackets is the proposed correction. Subscripts S and EA account for substrate (AISI 316) and
expanded austenite respectively. The elastic modulus of EA was obtained from the instrumented
hardness tests and the Poisson’s ratio was considered equal to the untreated substrate.
Modified Stoney’s formula proposed by Q. Wang et al. [4]:
1 E S d S2 ⎛ δ EA ⎞
σ0 = − ⎜1 − ⎟⎟ (C.3)
6 R δ EA ⎜⎝ dS ⎠
where the symbols have the same physical meaning as explained for the previous formulas.
Appendix C Page 267

XRD method proposed by Wagner et al. [5]:
The following expression was proposed to relate the stacking fault probability and the residual stress to
the results obtained in a Bragg-Bentano geometry:
a hkl = a 0 + a 0G hkl ⋅ α + a 0 (S1 )hkl σ + m ⋅ cos θ cot θ (C.4)
where ahkl is the lattice parameter measured from the XRD data, a0 is the lattice parameter of the
annealed specimen, Ghkl is the fault parameter (table C-1), α is the stacking fault probability, S1 is the
elastic constant (table C-1), σ is the residual stress, m is the slope of the line in figure 4.2-11 and the
value of cosθ·cotθ corresponding to ahkl, which is the extrapolation function used in the same graph.
The second order reflections allow distinguishing both effects, namely the stacking fault and the residual
stress, by making use of the following equation:
Δa hkl = a hkl − a hkl

app
= a 0Ghkl ⋅ α + a 0 (S1 )hkl σ − (a app − a 0 ) (C.5)
where the superscript app refers to the apparent lattice parameter from the extrapolation of the trend
line in figure 4.2-11 to cosθ·cotθ value of zero. For reflections (111) and (222), the second and third
terms on the right side of the equation are equal so that this relation can be derived:
Δa111 − Δa 222
= −0.0518 ⋅ α (C.6)
a0
The value of α can be obtained from equation C.6 and inserted in equation C.4, which allows calculating
the residual stress (table C-2)
Theory of thin plates and shells [6]:

Considering a thin plate as the one shown in figure C-1, and under the hypothesis of plane stress, i.e.
biaxial isotropic residual stresses:
σz = 0 (C.7)
σ x = σ y = σ (z ) (C.8)
Appendix C Page 268

The forces in the discs are balanced, but a bending moment is associated with the compressive residual
stresses present in the EA layer. Consequently, the forces and moments per unit width can be obtained
as:
d
f x = f y = ∫ σ ( z ) ⋅ dz = 0 (C.9)
0
d
⎛ d⎞
m x , m y = ∫ σ ( z ) ⋅ ⎜ z − ⎟dz ≠ 0 (C.10)
0 ⎝ 2⎠
where fx, fy and mx, my are the forces and moments per unit width respectively and d is the thickness of
the disc.
On condition that the displacements associated with the bending of the discs are small compared to
their thickness, and that the cross sections of the discs remain plane and rotate only with respect to the
neutral axes, the theory of pure bending of plates applies, and the strains ε can be defined as:
σx σy
εx = −ν (C.11)
E E
σy σx
εy = −ν (C.12)
E E
where E is the Young’s modulus and ν is Poisson’s ratio. The bending moments per unit width can thus
be defined as:
Ed 3 ⎛1 1⎞
mx = ⋅ ⎜ −ν ⎟ (C.13)
(
12 1 − ν 2 ) ⎜r
⎝ x r y ⎟⎠
Ed 3 ⎛1 1⎞
my = ⋅ ⎜ −ν ⎟ (C.14)
(
12 1 − ν 2 ) ⎜r
⎝ y r x ⎟⎠
And in this particular case, the disc is bent into a sphere sector, so that both radii of curvature are equal:
1 1
= = −ϕ ⇒ m x = m y (C.15)
rx ry
If we now consider the mean compressive residual stresses as the external load responsible for the
bending of the disc:
Appendix C Page 269

⎛δ + d ⎞ Ed 3 1
σ avg δ ⋅ ⎜ ⎟= ⋅ (C.16)
⎝ 2 ⎠ 12 ⋅ (1 − ν ) r
where σavg is the average residual stress, δ is the EA layer thickness, and replacing the values listed in
table C-3, σavg is found to be -0.770 GPa (sample ASPC P125B15).
If the stress distribution is approximated by a triangular distribution, and reducing the moments to the
layer core interface it is obtained:
⎛ δ ⎞ ⎛2 ⎞ ⎛δ ⎞
⎜ σ surf ⎟ ⋅ ⎜ δ ⎟ = (σ avg δ ) ⋅ ⎜ ⎟ (C.17)
⎝ 2⎠ ⎝3 ⎠ ⎝2⎠
3
σ surf = σ avg (C.18)
2
Using the previous calculated values, equation C.18 yields σsurf = -1.155 GPa. A similar procedure is
followed to calculate the residual stress profiles from GDOES carbon distribution and LBC strain
hardening, yielding maximum residual stresses of -1.22 GPa and -1.61 GPa respectively.
Figure C-1: Schematics of the thin discs used for the assessment of residual stresses (cross
section): δ - expanded austenite layer thickness; d - disc thickness
Appendix C Page 270

Table C-1: Fault parameters and elastic constants for different reflections [7]
hkl Ghlk x 102 (S1)hlk x 105
111 -3.45 -0.97 kg/mm2
200 +6.89 -2.97 kg/mm2
220 -3.45 -1.47 kg/mm2
311 +1.25 -2.03 kg/mm2
222 +1.73 -0.97 kg/mm2
Table C-2: Data used for the calculation of the residual stress on sample ASPC P125B15
hkl ahkl aapp a0 α m cosθ·cotθ σ
111 3.678 Å 3.6929 Å 2.39

3.68679 Å 0.0602 0.00255 Å 1.98 GPa
222 3.685 Å 3.6884 Å 0.65
Table C-3: Parameters used for the calculation of residual stresses from the bending of thin discs
Parameter Symbol Value
Young’s modulus E 205 GPa
Poisson’s ratio ν 0.305
Disc thickness d 530 μm
Layer thickness δ 20 μm
Radius of curvature r 0.8962 m
Appendix C Page 271

List of references for appendices A, B and C
1. Corujeira Gallo, S., Machavaram, V. R., Fernando, G. F. and Dong, H.: Probing active screen
plasma using high-temperature optical fibre assisted OES method, PSE 2008 (2008) Garmisch-
Partenkirchen, Germany,
2. British Standard DD CEN/TS 1071-11:2005, 2005, "Advanced technical ceramics - Methods of

test for ceramic coatings", BSI, London, www.bsi-global.com
3. Mezin, A.: Coating internal stress measurement through the curvature method: A geometry-
based criterion delimiting the relevance of Stoney's formula, Surface and Coatings Technology
(2006) 200, 18-19, 5259-5267
4. Wang, Q., Ishikawa, H., Nakano, S., Ogiso, H. and Akedo, J.: Curvature-based residual stress
measurement for ion-implanted stainless-steel sheet, Vacuum (2004) 75, 3, 225-229
5. Wagner, C. N. J., Baisseau, J. P. and Aqua, E. N.: X-Ray diffraction study of plastically
deformed copper, Transactions of the Metallurgical Society of AIME (1965) 233, 7, 1280-1286
6. Timoshenko and Woinowsky-Krieger: Theory of plates and shells, 2nd Ed. (1959) London,
McGraw Hill
7. Sun, Y., Li, X. Y. and Bell, T.: X-ray diffraction characterisation of low temperature plasma
nitrided austenitic stainless steels, Journal of Materials Science (1999) 34, 19, 4793-4802
Appendices Page 272

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ACTIVE SCREEN PLASMA SURFACE ENGINEERING OF AUSTENITIC STAINLESS STEEL

FOR ENCHANCED TRIBOLOGICAL AND CORROSION PROPERTIES

by SANTIAGO CORUJEIRA GALLO

The University of Birmingham

for the degree of

School of Metallurgy and Materials

College of Engineering and Physical Sciences

The University of Birmingham

This unpublished thesis/dissertation is copyright of the author and/or third

Any use made of information contained in this thesis/dissertation must be in

improved surface quality achieved with the former.

carburising relies on plasma activation and moderate ion bombardment.

additional charged particles and their electrostatic confinement.

CHAPTER 2: LITERATURE REVIEW 3

CHAPTER 3: EXPERIMENTAL PROCEDURES 57

CHAPTER 5: INTERPRETATION AND DISCUSSION 94

CHAPTER 6: SUMMARY AND CONCLUSIONS 132

CHAPTER 7: PROPOSALS FOR FUTURE WORK 136

LIST OF REFERENCES 137

FIGURES AND ILLUSTRATIONS 175

Table 2.3-1: Typical commercial austenitic stainless steels compositions

Figure 2.1.1-1: Historical evolution of materials and their relative importance

AFM Atomic Force Microscopy

and environmental friendliness. DC plasma thermochemical treatment is a well-established technology,

Chapter 1: Introduction Page 1

performance of the substrate.

present project are the following:

steel, to form carbon expanded austenite.

bias) on the ASPC process and optimise it.

 To conduct systematic characterisation on ASPC treated materials.

Chapter 1: Introduction Page 2

1.1. Introduction, history and development

the information is not as reliable as the other three charts.

Chapter 2: Literature review Page 3

industries, in Europe and in the United States.

surface and exert the characteristic resistance to corroding agents [4].

Chapter 2: Literature review Page 4

manufacturing characteristics [5].

% Ni ⋅ equivalent = (Ni ) + (Co ) + 0.5 ⋅ (Mn ) + 0.3 ⋅ (Cu ) + 25 ⋅ (N ) + 30 ⋅ (C ) (2.1-2)

Chapter 2: Literature review Page 5

engineering alloys, heat treatments play an important role in this regard.

Some of them will be briefly introduced in the following sections.

1.2.1. Martensitic stainless steels [5-8]

Chapter 2: Literature review Page 6

toughness and ductility.

precipitation of intermetallic compounds provides an alternative hardening and strengthening

hydroelectric power generation and aeronautic applications.

Chapter 2: Literature review Page 7

challenges associated with such requirements.

tempering resistance and Ti, Al, Cu and Co to induce precipitation hardening.

transformable and precipitation hardened condition.

stainless fasteners, wire and cables.

Chapter 2: Literature review Page 8

embrittlement by martensitic transformation of the retained austenite present at grain boundaries in

of these alloys: their low toughness.

also soft and can get easily marked.

Chapter 2: Literature review Page 9

making them interesting for applications in chemical plants.

1.2.4. Duplex stainless steels [5-9]

To conduct systematic characterisation on ASPC treated materials.

Enhanced functional performance and higher productivity

Use of cheaper substrate materials