Nitriding

Chart of Fe – N and nitrides

Nitride Fe4N with CFC grid.
Also γ´ phase.
Hardness of 450-500 HV.
C its occurrence strongly limits.
Nitride Fe2-3N with HCP grid.
Also ε phase. Very stable in
wide range of N content.
Hardness of 250-300 HV.
By higher C, arises
carbonitride Fe2-3 (C, N),
which is more fragile and has
a hardness of 400-450 HV.
Nitride Fe2N, brittle and
undesirable.
Eutectoid at 590 oC, brownit.
Very brittle and undesirable.
 Ferrite with nitrogen
Pure ferrite - dissolves
max 0.11 % N.
With decreasing
temperature solubility
decreases
up to 0.004 % N
at room temperature.
In the presence of
additional impurities,
especially W, Mo, ​Cr, Ti
and V, strongly
increases the solubility
of nitrogen in ferrite,
up to 3 %.
Typical nitrided layer
Metalography of layer
Too high temperature
Change to na brownite !
 Hardness of carbon steel
after nitriding
In carbon steel, all
nitriding phase are less hard
than normal martensite.
In order to obtain as a result
nitriding hard surface, shall be
present in the steel alloy,
creating hard nitrides :
- Al, Ti, Cr, Mo - steel nitriding.
Typical hardness of that nitriding
steels can reach up to 1300 HV.
In the nitride layer, possibly in
ferrite just below it, then are
needles of alloy nitrides.
Hardening after nitriding does not
make sense
 Influence of alloys
hardness grows, depth decreases
 Purpose of nitriding
Unlike carburising far more versatile :
- increase surface hardness
- increase abrasion resistance
- reduce the coefficient of friction
- increase corrosion resistance
(excluding Stainless steel)
- improve fatigue properties.
Properties of surface phases
Pure ferrite with dissolved nitrogen
(so-called diff use layer) - layer is softer,
less resistant to abrasion, but has
excellent toughness and resistance to
fracture. It also increases the fatigue
strength.
γ´ phase ... is the most abrasion resistant,
has the highest hardness is relatively
tough
ε phase .... It is more fragile, has a very
low coefficient of friction, has a high
resistance to corrosion, but less abrasion
resistance.
 Options to control
composition of layer
Surface composition strongly depends on the
composition of nitrided steel.
Carbon steel promotes the formation of
ε nitride and suppresses the production of
nitride γ′ .
For various purposes, it would be good to
control composition of the coating layer
through composition of atmosphere, but
these options are severely limited.
We can best control the composition of the
surface layer during glow discharge
nitriding .
Different surface layers
Basic conditions of nitriding
Conventional nitriding temperatures are
450 to 590 oC. Under very slow diffusion
of nitrogen, above brownit arises.
Slow diffusion nitriding = Thin layer.
Exceptionally nitridation even at a higher
temperature, if does not matter excessive
fragility of layer - Eg corrosion nitriding.
Nitrogen in the molecular state of N2
can not diffuse into the steel surface.
Must have nitrogen atoms or ions.
 Salt bath nitriding
Nitriding is carried out in molten salts
- the main component is cyanides and
cyanates. Bearers of nitrogen are radicals
-CN,-CNO,-NO3
Offer of nitrogen is large, the method is
very simple and fast
Due to the toxicity of cyanide, this method is
now virtually everywhere prohibited.
A small amount can be used for nitriding
molten ferricyanides or ferrocyanides
(blood salt).
In search of new suitable salt – organic.
Nitriding in gas - ammonia
Nitriding at atmospheric
pressure.
Ammonia is partially
decomposed
(catalytically)
in a special retort.
It was formerly the most
common nitriding
method.
Relatively poorly
controllable
 Nitrogen probe HydroNit
Attempts to introduce a potential of nitrogen
atmosphere.
Patent of company IPSEN.
Recombination of molecular hydrogen is faster than
nitrogen, can write the equation:
NH3 → [N] + 3/2 H2
Not quite right - it is not a reversible reaction.
Then the nitrogen potential CN = p (NH3) / P (H2)3/2
The partial pressure of hydrogen is captured with
HydroNit special probe.
It should also be familiar with the overall
composition and pressure of the inlet
atmosphere to calculate the partial pressure
of ammonia.
Probe Hydronit
 Phase chart Fe – N
for nitrogen potential
Depth of gas nitriding
 Vacuum nitriding
Nitriding atmosphere is composed from
nitrogen, ammonia and nitrous oxide N2O
(laughing gas).
N2O acts as activator of nitriding. Cleaves
molecular nitrogen on the surface of
steel and diffuses into it.
Emerging nitriding layer is porous, and
always contains a certain amount of
oxygen.
The process is patented under the names
ALNAT N or NITRAL.
Diffusion rate higher than in gas nitriding,
but lower than in glow discharge.
 Plasma nitriding
Nitriding in an anomalous glow discharge.
Also known as ion or plasma nitriding.
Modern nitriding method, carried out in a
vacuum.
Nitrogen is present in the form of ions,
may very well diffuse to the steel surface.
It is faster than in the nitriding gas.
It is also better regulated.
Detailed description will be given in the
context with anomalous glow discharge.
Comparison of nitriding
speeds
 Ternary diagram Fe – C - N
The present
diffusion of
carbon and
nitrogen
mutually
supports
- higher
speed
and depth.
Relationship between ternary
and binary diagram
Low temperature carbonitriding
Atmosphere as by nitriding, but enriched with
carbon source - usually a small amount of a
gaseous hydrocarbon.
Takes place at the same temperatures as nitriding,
but it is faster.
Formed on the steel surface carbonitride ε,
or carbonitride of alloying elements.
Nitride γ' dissolves little in amount of carbon,
is strongly suppressed.
But ε carbonitride layer is much thicker than by the
nitriding.
After carbonitriding has been steel only slowly
cooled.
 High temperature
carbonitriding
It is basically carbirising.
Takes place at the same temperatures as
cementation.
Diffusion of carbon in steel is accelerated by the
current diffusion of a small amount of nitrogen.
Carburizing atmosphere is enriched by the nitrogen
source, usually a small amount of ammonia.
Nitrogen affects only accelerating the diffusion of
carbon, a small amount is dissolved in austenite
and in steel structure is not observable.
Must be followed by quenching and tempering
as well as after hardening.
 Other combined methods
► Sulfonitriding – imultaneous diffusion
of sulfur during nitriding to improve
frictional properties.
Sulfides have a low coefficient of friction.

► Oxinitriding –known as PRONOX

- Strengthening the nitriding layer
often in a vacuum in an atmosphere
of CO2 or H2O.
Improved frictional properties, especially
due to the increased porosity of layers,
which then easier to keep lubricating oil.
Example of oxinitriding