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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
Research objectives
Experimentation Equipment
Future work
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
(After J.R. Davis, Surface Engineering for Corrosion and Wear Resistance, ASM International, 2001)
35
11
Iron Atoms
Nitrogen Atom
X Unoccupied Interstices
(After D.H. Jack, Carbides and Nitrides in Steel, Materials Science and Engineering, 1973)
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
VN uN,γγ’/αα
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)
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
(After M. Bever, Case Hardening of steel by nitriding, ASM Source Book on Nitriding, 1977)
Gas circulation
path
Metallurgical requirements
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)
100 250 µm
Fe-
Nitride
Hardened
Case
Substrate
Core
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
50 µm