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VAC AERO

I N T E R N A T I O N A L I N C.

Gas Nitriding:
An Industrial Perspective

By Jerome Darbellay
Supervisors: Drs D. Embury and H. Zurob

MSE 701 Seminar Department of Materials Science and Engineering


March 22, 2006 McMaster University
Outline
 Review of gas nitriding process

 Research objectives

 Fe-N diagram and process equilibrium

 Nitride layer growth model for pure iron

 Experimentation Equipment

 Nitrided Case Evaluation

 Future work

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Fundamental of Nitriding
 Thermochemical treatment producing enhanced surface
properties from the bulk properties
 Case hardening results from diffusion of N into substrate (solid
solution) and precipitation of nitrides (FeN and alloy elements
nitrides) when holding the metal at suitable temperature
(generally below 575°C)
 Ammonia (NH3) is nitrogenous gas typically used since it is
metastable at nitriding temperature and decomposes on contact
with iron
 Quenching is not required for production of a hard case
 Process methods include: gas, liquid (salt bath) or plasma (ion)
 low alloy steel (4140), depth of case [µm]
Gas Plasma Salt Bath
200 210 205
(525ºC, 4hrs) (475ºC, 3hrs) (575ºC, 2hrs)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 3


Liberation of nascent N
H
Possible reactions taking place at the steel
N
surface: H
H H
N

Atmosphere
(catalyst) H H H

2NH3 ——
(heat)
> 3H2 + 2N (dissolved N
in α-Fe) H H

Adsorption
——> 3H2 + N2 (gas)

Adsorption
N
H

layer
N N Recomb. Recomb. H H

——> N2 + 6H (dissolved N
H

in α-Fe)

Diffusion

Steel
N

Diffusion

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 4


Advantages of Nitriding
 Relatively low-temperature process when compared to other case
hardening process such as carburization (C diffusion), carbonitriding (C
and N diffusion)
 No quench requirement, thus reducing distortion
 High hardness value obtained with this family of steels (above 1000HV,
700HV ≈ 2200 MPa UTS):
 low-alloyed steels 0.5C, Ni, Cr, Mo, Mn, Si, Al (Nitralloys,
4340,4130,…)
 die steels 0.4C-5Cr-Si-Mo (H11, H12 & H13)
 tool steels 0.5-1.5C-Cr-Mo-W-Va (A-2, D-2, Mo, S-7,…)
 Resistance to corrosion (for alloyed and tool steels). Corrosion
resistance grows in the order of γ’-nitride, ε- nitride and ε-carbonitride
 No change to core properties

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 5


Cost of Nitriding
Approximate cost for low-alloyed steel family:
 $2/lb for 0.005” case (~ 5hrs, no evaluation coupons) to $10+/lb for

0.025” case (~25hrs, acceptance coupons included)

(After J.R. Davis, Surface Engineering for Corrosion and Wear Resistance, ASM International, 2001)

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Applications of Nitriding
 Principal reasons for nitriding:
 High surface hardness
 Wear / abrasive resistance and anti-galling properties
 Improve fatigue life (compressive stress at surface)
 Improve corrosion resistance (except for SS material)
 Improve resistance of surface to softening effect of
heat up to nitriding temperature
 Typical applications:

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Limitations of Nitriding
 Distortion occurring in the form of growth (compound layer
formation) and increase in volume in the case
 Nitriding can also act as stress relief/tempering operation if not
previously performed, leading to unexpected distortion
 Uniform case hardening can only be obtained through continuous
controlled circulation (preferably by use of internal fan), accurate
control of process gas and temperature and proper part preparation
(cleaning, blasting, handling)
 Ammonia is used in a very wasteful manner (typically up to 70% is
vented) and large percentage of N atoms liberated will combine to
form inert N2. This gas, as well as formed H2 are also vented.
 Nitriding of SS material requires removal of noble oxide layer
(depassivation using ammonium chloride (NH4Cl) ). Nitrided SS
components will exhibit a significantly reduced corrosion resistance
due to precipitation of CrN

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Objectives of Research
 Problem
 Nitrided case microstructure and properties of industrial alloyed
steels can not precisely be modeled to optimize the nitriding
parameters
 Objectives
 Compile database of N diffusion parameters and models for gas
nitriding of pure iron and alloyed steels currently available in
literature
 Combined experimental and modeling activities to explore the
various microstructure produced during gas nitriding of iron alloyed
with C (and other selected alloying elements) to be compared to
mechanical properties of hardened case
 Combined experimental and modeling studies of the detailed
evolution of the nitride layer in alloyed steel and its subsequent
relation to the process parameter
 Interaction of Industrial Project with McMaster University
 Development of models related to carefully defined compositions
 Range of experimental techniques available for characterisation of
nitrided metals

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 9


Fe-N Phase Diagram

35

11

(Adapted from D.T. Hawkins, ASM Source Book on Nitriding, 1977)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 10


Phases in the Fe-N system
Interstitial
Phases Composition Wt. % (At. %) N atoms per 100 Bravais Lattice
Fe atoms
Ferrite (α) Fe 0.10 (0.40) - B.c.c.
Austenite (γ) Fe 2.8 (11) 12.4 F.c.c
Martensite (α’) Fe 2.6 (10) 11.1 B.c. tetrag.
γ’ Fe4N 5.9 (20) 25 Cubic
ε Fe2N1-x 4.5-11.0 (18-32) 22 - 49.3 Hexagonal
ζ Fe2N 11.4 (33.3) 50 Orthorhombic

Fe4N crystal structure

Iron Atoms

Nitrogen Atom

X Unoccupied Interstices

(After D.H. Jack, Carbides and Nitrides in Steel, Materials Science and Engineering, 1973)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 11


Nitriding Gas – Pure Iron Equilibrium Diagram
700 600 550 500 450 400 o
C
1 .5 3 1 .6

1 0 .0 0 % N %N
ε 1 7 .8

1 9 .7 5 1 0 .0
9 .5 0
5 .6
Fe - N 9 .2 5
9 .0 0
5 .8 9 7

)
3 .2

-1/2
0 .5 (Wt. %N)

)
8 .7 5

-1/2
8 .5 0 5 .8 9

log (K N ) (atm

K N (atm
γ'
8 .2 5 1 .8
0 5 .8 7 % N 1 .0
5 .8 5

5 .8 2
-0 .5 5 .7 8 0 .0 1 0 .3
(E. Lehrer, Z. Electrochemie, 1930) 5 .7 3
0 .0 3 % N
0 .0 7
α 0 .0 0 5
-1 0 .1
γ
0 .0 5
0 .0 0 1

-1 .5 0 .0 3
1 .0 1 .1 1 .2 1 .3 1 .4 1 .5 x 1 0 -3 1 /K

Typical Nitriding Temperature Range


(L. Maldzinski, New possibilities for controlling gas nitriding…, Surface
Engineering, 1999)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 12


Monolayer growth in binary system (1)
 Diffusion of solute (N) governs the growth kinetics. Flux
balance equation at the γ’/α interface is given by:
vγ '/ α γ '/ α α /γ ' γ' α uN
γ'
(u N − u N ) = J N − J N uN,s/γγ’
J Nγ '

VN uN,γγ’/αα

vγ '/ α is migration rate of γ’/α interface


γ’ α
VNγ ' is partial volume/mole of N atom of γ’ phase
u γN'/α , uαN / γ ' contents of N on the γ’ and α side of J Nα
interface uN,αα/γγ’
γ' α
JN , JN diffusion fluxes of N on the γ’ and α side of lγ '
interface Distance from surface z
 The following assumptions are made:
 Planar interface parallel to surface
 Growth of new phase obeys parabolic growth (i.e. l = k t where l is thickness of
layer, t is time and k is called growth rate constant)
α
 α substrate is saturated with N (i.e. J N = 0 )
 Diffusion in γ’ is stationary due to narrow composition range in the phase
 Mobility MN is independent of concentration
(H. Du, Gaseous Nitriding Iron - Evaluation…, Z. Metallkd., 1995)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 13


Monolayer growth in binary system (2)
 The partial Gibbs free energy (=chemical potential) of N is the driving force
for diffusion. The chemical diffusivity DɶN can be related to the self diffusion
coefficient DN* using the thermodynamic factor Ψ :
u N ∂µN uN,µN N concentration and chemical potential
DN = DN Ψ = DN ⋅
ɶ * *
R gas constant
RT ∂u N T absolute temperature

γ'
N ∂u N
γ' Dɶ
 Using Fick’s first law of diffusion for flux:
JN = γ '
VN ∂z
 Integrating over the thickness of layer and applying stationary diffusion
assumption (constant flux over system):
l uγN '/ α
uγN '/ s N content at the surface γ' 1
J N ∫ dz = − γ ' ∫ Dɶ Nγ ' du N
0
VN uγN '/ s
(H. Du, Gaseous Nitriding Iron - Evaluation…, Z. Metallkd., 1995)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 14


Multiphase growth in binary system (1)
 The treatment of a diffusion-controlled growth of a bilayer in a binary metal-
interstitial system is defined analogously as for the case of monolayer
growth. Applying Flux balance equation at both the ε/γ’ and γ’/α interface
yields: uN
ε /γ ' uN,ε/
,ε/s
,ε/
J Nε
v ε /γ ' γ '/ ε ε γ'
ε/γ’: ε
(u N − u N ) = J N − J N
uN,ε/γ
,ε/γ’
,ε/γ
uN,γ,γ’/ε
,γ ε
J Nγ '
VN uN,γγ’/αα
vγ '/ α γ '/ α α /γ ' γ' α ε γ’ α
γ’/α: (u − u ) = J − J
VNγ '
N N N N
J αN
uN,αα/γγ’
lε lγ '
φ
N ∂u N
φ Dɶ Distance from surface z

Where JN = φ (φ = ε , γ 'or α )
VN ∂z
 The following assumptions are made:
 Stationary diffusion may not be satisfactory for ε phase due to it’s wide range of composition (-
> flux balance equation to be solved numerically)
 Self-diffusivity of ε is likely to be concentration dependent for the same reason

(H. Du, Gaseous Nitriding Iron - Evaluation…, Z. Metallkd., 1995)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 15


Complications from pure Iron kinetic model
 Nitride layer nucleation
 Most models assumes an equilibrium concentration of N with the
atmosphere, but the formation of a compact nitride layer is
retarded by:
a) Incubation time for nucleation
b) Time for nuclei to coalesce into a compact layer
 Effect of C content
 Affect N activity (coefficient of diffusion) in α-Fe and ε-nitride
 Complex phases transformation (i.e. case of θ cementite -> ε
carbonitride -> γ’ in α at α/γ’ boundary)
 Effect of alloying elements
 Both nitride (Cr, Mo, Al, V, Ti) and non-nitride (Ni) forming
elements reduces N diffusion coefficient in a-Fe
 Reaction of nitride forming elements with N to form stoichiometric
nitrides
 Do we have both external and internal nitriding?

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 16


Nitriding Furnace Schematic

(After M. Bever, Case Hardening of steel by nitriding, ASM Source Book on Nitriding, 1977)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 17


Vac Aero Gas Nitrider

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 18


Vac Aero Nitriding Retort
 Retort, fixturing basket and internal liner all
made of IN 600 material
0 0.25 0.5 m

Gas circulation
path

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 19


Process Control
 Good process control improves:
 Process repeatability and economics

 Metallurgical requirements

 Operator interfacing, data trending and archiving

 Key Control in nitriding


 Temperature (± 15ºF per AMS 2759/6 Gas Nitriding
Specification) by means of T/C and SPP
 Process gas by means of flow meter. Anhydrous ammonia
and nitrogen shall be of the high purity grade (99.98%)
with dew point -54ºF (-48ºC) or lower.
 Atmosphere by means of a dissociation pipette (burette) (±
15% dissociation per AMS 2759/6) or gas analyzer
 Retort pressure (slightly above atmosphere to prevent any
O2 to enter vessel (risk of explosion) and maintain flow
through pipette or gas analyzer

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 20


Nitriding Potential
 Nitrogen solubility at the surface of the iron is
determined by equilibrium:

NH 3 ⇔ H 2 + [N ] (dissolved in Fe )
3
2
hence (for dilute solution of N in Fe, Henry’s law)
pNH 3
[a N ] = [% N ] = k ⋅
pH 2 3 / 2
where k is an equilibrium constant at a given
temperature and pNH3 and pH2 are the partial pressure
in the gas
pNH 3
 Nitriding potential definition: KN =
pH 2 3 / 2
MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 21
Atmosphere Control - Burette
 Gas dissociation is simply the amount of decomposition of the
ammonia gas. The exhaust gas is a mixture of 2NH3 + H2 +
N2 and ammonia is the only one soluble in water.

H2O
H2O
H2O

(D. Pye, Practical Nitriding and Ferritic Nitrocarburizing, ASM International, 2003)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 22


Atmosphere Control – H2 Gas Analyzer
NH3 Atmosphere
dNH3
expanded
Dissociation
Dissociated = 2α
Rate = d = H2 = h = 0.75d
NH3 = α
2α/(1+α) d
N2 = n = 0.25d

NH3 A’ = A-α r=A–d=


=A A-α/(1+α) r

Inlet Atmosphere After Dissociation Normalized Outlet


Atmosphere (volume =1)
B. THE METHOD:
Burette
1. Measure %H2 using the analyzer: h Logic
2. Calculate Dissociation Rate d: d = h/0.75
3. Calculate α as a function of dissociation d: α = d/(2-d)
4. Calculate Residual NH3: r=1–d
r 1− d
Kn = =
5. Determine Nitriding Potential: h3/ 2 (0.75 ⋅ d )3 / 2

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 23


Precision of Control
 Control System
 Precision of Gas Flow Regulation
1) AMS Standard 2759/10 for automatic control of gas
nitriding by Kn requires precision of ± 10% at setpoint
2) An error of 2% in the analysis of the H2 content of the
exhaust gas translates into an error of about 20% for
KN for the low KN setpoints required to achieve zero
compound layer (Fe-Nitride)
3) Original flow regulation (motor driven needle valve)
supplied with the control panel was not suitable
(precision of ~ 4%)

 New gas regulations relies on Mass Flow Controller


with precision better than 1%

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 24


Precision of Control
 Error on H2 measurement – Effect on KN Control

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 25


Samples Evaluation Method
Case properties to
Method
be evaluated
Fe-Nitride Layer - Light Microscopic Analysis (LMA), by etching
Thickness - Scanning Electron Microscopic (SEM) analysis
- Light Microscopic Analysis, by etching
- Scanning Electron Microscopic analysis
Depth of case
- Microhardness Profile
- Methods used for N concentration as a f(depth)
- Light Microscopic Analysis with positive phase contrast microscopy of
the etched samples
Phase Identification - Scanning Electron Microscopic analysis
- X-Ray Diffraction (phase concentration)
- Transmission Electron Microscopy (TEM): Diffraction Pattern
- Electron Probe X-ray Micro-Analysis (EPMA)
- Focused Ion Beam (FIB)
- Glow Discharge Spectroscopy (GDOES): qualitative only, quantitative
N concentration as a possible using standard of known N content
f(depth) below surface - Transmission Electron Microscopy (TEM): Electron Energy-Loss
Spectroscopy (EELS)
- X-Ray Diffraction (XRD): lattice parameters -> N concentration
- Chemical Analysis: total N concentration

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 26


Samples Evaluation (1)
 Microhardness profile: Effective and Total Case Depth

100 250 µm

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 27


Samples Evaluation (2)
 Microstructure of Nitralloy 135M (0.4C-0.6Mn-0.3Si-1.6Cr-
0.35Mo-1.2Al), quenched and tempered, Nital etched

Fe-
Nitride

Hardened
Case

Substrate
Core

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 28


Samples Evaluation (3)
 Microstructure of SAE 1006 (0.08C- Fe-
Nitride
0.3Mn): Automotive Seat Rails
application
Substrate

Fe-
 Microstructure of SAE 1144 (0.45C- Nitride
1.5Mn-0.25Si): Throttle Valves
application Substrate

Fe-
 Microstructure of SAE 4140 (0.40C- Nitride
1.0Cr-0.85Mn-0.25Si-0.2Mo):
Automotive Shafts application Substrate

(Adapted from www.nitrex.com website)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 29


Samples Evaluation (4)
Fe-
Nitride

 Microstructure of H13 Hot-work


Tool Steel (0.4C-5Cr-1.3Mo-1V), Hardened
Case
Quenched and Tempered, Nital
Etched: Forging Dies application

50 µm

 Microstructure of ASTM A1011


Commercial Steel Type B (Fe-
0.04C-0.26Mn), Nital Etched:
Part Manufacturing application
Fe-
Nitride
50 µm

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 30


Samples Evaluation (5)

 Phase Identification by means


of LMA with positive phase
contrast microscopy of an Fe
sample etched with 1 pct Nital
+ 0.1 vol pct HCl

(H. Du, Microstructural and Compositional


Evolution…, Metall. Trans. A, 2000)

 Nitrogen content as a function of depth


below the surface determined with EPMA
in layers obtained on an Fe specimen

(H. Du, Microstructural and Compositional


Evolution…, Metall. Trans. A, 2000)

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 31


Future Work
 Comprehensive literature review of detailed structures
and properties for a variety of nitrided steels
 Review the formation of a compact Fe-nitride layer by
nucleation and coalescence as well as the formation
of multilayer Fe-nitride
 Study the effect of C content on the kinetic of nitride
layer growth: experiments with carefully defined steel
microstructures such as spheroidized carbides,
samples with C gradient a surface (decarburized)
 Study the effect of alloying elements (such as Cr, Al)
on the kinetic of Fe-nitride layer growth and
mechanical properties of nitrided case

MSE 701 - March 22, 2006 Gas Nitriding: An Industrial Perspective 32