Surface Hardening:

Thermochemical Heat Treatment

Dr. Santosh S. Hosmani
DEPT. METALLURGY & MATERIALS SCIENCE,
COLLEGE OF ENGINEERING, PUNE 411 005
Nitriding Nitriding
Nitriding
Nitriding methods: gaseous nitriding, plasma nitriding and salt bath nitriding.
E i t d t f it idi th th d Eminent advantages of gaseous nitriding over other methods:
- precise control of chemical potential of nitrogen in the nitriding atmosphere by controlling the
gas flow rate of ammonia and hydrogen, i.e. nitriding potential.
- Can be an economical for wide-range of size of the workpieces. Can be an economical for wide range of size of the workpieces.
But, each method has its own advantages and limitations..
Now, discussion about nitriding-aspects will be by using gaseous nitriding method.
Widely used temperature-range for Gaseous Nitriding of Fe-based alloys: 500 590C
Fe-N phase diagram
Nitrogen has an atomic diameter of 0.142 nm and is dissolved in iron in
i t titi l iti i t h d l id f th bi l tti th t h interstitial positions in octahedral voids of the cubic lattice that have a
maximum diameter of 0.038 nm in bcc alpha () iron and a maximum
diameter of 0.104 nm in fcc gamma () iron.
- Fe
3
N
1+x
hcp bcc
Orthorhombic zeta
(), Fe
2
N, forms at
temperatures below
500 C and nitrogen
fcc-type arrangement of
the iron atoms
500 C and nitrogen
contents exceeding
11 wt%conditions
that are not used in
nitriding practice nitriding practice.
In case of carburizing, the downside of the deep case, of course, is the occurrence
Carburizing versus Nitriding
g, p , ,
of grain growth, which is inevitable due to the extended cycle time at elevated
temperatures for the carburizing procedure.
Nitriding takes place in the ferrite region on the iron-carbon equilibrium diagram, g p g q g ,
which means that grain size in both the surface and the core is not affected.
However, the same deep case achieved by carburizing cannot be accomplished
by nitriding. Once the cycle time extends beyond 90 h, there is no commercial or y g y y
metallurgical advantage to be gained.
With conventional surface diffusion process techniques such as carburizing and
carbonitriding, the steel must be at a suitable austenitizing temperature g g p
(depending on the steel composition) after carburizing, followed by quenching (or
rapid cooling) to transform the austenite phase (FCC lattice) into martensite (BCT
lattice). Hence, distortion is the issue.
Nitriding is a relatively low-temperature process and produces a shallower case
than does carburizing. Most importantly, no quench is involved. On completion
of the process, the steel can be cooled down naturally under its atmosphere or
force cooled using clean dry nitrogen Generally the steel is allowed to cool force-cooled using clean, dry nitrogen. Generally, the steel is allowed to cool
naturally, thus reducing the risk of thermal gradients due to sectional changes.
If the engineer can live with extended cycle times, the nitriding process
can offer many distinct advantages:
Red ced distortion (like t isting and bending that leads to shape Reduced distortion (like, twisting and bending that leads to shape
change)
Improved part cleanliness
Reduced final machining time Reduced final machining time
Improved dimensional stability
If one considers the cost of scrap due to distortion and time spent If one considers the cost of scrap due to distortion and time spent
straightening, nitriding is not an expensive process compared to
carburizing.
However, in terms of high-volume production requirements (e.g.,
automotive gears), nitriding does not always present a viable option.
Do not be misled into thinking that the nitriding process causes absolutely
no distortion. It is a question of the definition of distortion. Distortion
resulting from the nitriding process takes the form of uniform growth at the
immediate surface.
When another element or combination of elements is added to create
changes in surface chemistry, volume changes will occur in the form of size
change and uniform growth. For example, a ring will grow in terms of g g p , g g
outside and inside diameters, the net effect being that the bore diameter
decreases
Basic reactions in gaseous nitriding:
Gaseous Nitriding
] N [ N
2
1
2

3 1
2 2 3
H
2
3
N
2
1
NH +
H
3
] N [ NH +
2 3
H
2
] N [ NH +
Nitrogen has an atomic
di t f 0 142 d diameter of 0.142 nm and
is dissolved in iron in
interstitial positions in
octahedral voids of the
cubic lattice that have a
maximum diameter of
0.038 nm in bcc alpha ()
iron and a maximum iron and a maximum
diameter of 0.104 nm in
fcc gamma () iron.
Nascent nitrogen has a strong affinity for iron and steel at elevated
temperatures and will readily diffuse. The higher the temperature to which
Ref.: Book by David Pye
the steel is elevated, the faster and deeper the nitrogen diffusion occurs.
B i ti i it idi Nit idi t
Gaseous Nitriding
Basic reactions in gaseous nitriding:
] N [ N
2
1
2

Nitriding parameters:
Nitriding temperature
Nitriding potential
2 2 3
H
2
3
N
2
1
NH +
3
Nitriding potential
Lehrer diagram (for pure Fe)
2 3
H
2
3
] N [ NH +
Lehrer diagram (for pure Fe)
2 / 3
H
NH
n
2
3
p
p
r = nitriding potential
- Fe
3
N
1+x
hcp
fcc-type arrangement
bcc
fcc type arrangement
of the iron atoms
Gaseous Nitriding
Schematic presentation of the surface region of a nitrided iron/iron-based alloy
N from NH
3
/ H
2
gas mixture
Fe N -Fe
2-3
N

|
-Fe
4
N
compound
layer
tribological
anti-corrosion
properties
white layer
interstitial N
and/or diffusion
In -Fe
matrix
fatigue properties
MeN
n
precipitates zone
fatigue properties
FIGURE: Pure iron nitrided, etched
with Nital.
FIGURE: Pure iron nitrided,
SEM micrograph.
The nitride layer shows pores that, according to pressure theory, form
h it t i th it id l bi t it l l when nitrogen atoms in the -nitride layer recombine to nitrogen molecules,
thus creating high pressures.
The nitrides begin their formation by the
nucleation of at the immediate steel
surface interface with the nitriding surface interface with the nitriding
atmosphere. This nucleation process
progresses and continues until the
subsequent nucleation of at the steel q
surface interface. Note that the nitrogen
diffusion is much slower in the compound
layer than in the steel substrate.
Gaseous Nitriding
gas atmosphere
(NH
3
+H
2
)
Fe-N phase diagram

fcc

- Fe
3
N
1+x
hcp bcc
fcc
x
fcc-type
arrangement of the
iron atoms
y
/gas o
n
Concentration depth-profile

y
/gas
y
/
y

g
e
n

c
o
n
c
e
n
t
r
a
t
i
o
Depth below the surface

N
i
t
r
o
g
gas atmosphere
(NH
3
+H
2
)

y
/gas o
n
Concentration depth-profile

y
/gas
y
/
y

g
e
n

c
o
n
c
e
n
t
r
a
t
i
o
Depth below the surface

N
i
t
r
o
g
Carbon manipulates the amount of and formed within the surface structure. In
a typical nitriding steel with a carbon content of approximately 0.4 wt%, the
formation of to will be roughly equal using the gas nitriding process The formation of to will be roughly equal using the gas nitriding process. The
higher the carbon content of the steel, the greater the -phase in the compound
layer. The lower the carbon content, the greater the -phase.
The overall thickness of the compound zone ( + ) is a function of time,
temperature, and pressure (usually atmospheric pressure). The amount of carbon
in the steel has a small effect on thickness. Again, however, carbon content
considerably affects the composition of the compound layer determining whether considerably affects the composition of the compound layer, determining whether
the layer will be predominantly , , or equal amounts of each phase. If the
compound layer thickness is a critical issue, then the steel must be selected
carefully to accomplish the required surface metallurgy.

Ref.: Book by David Pye

Gas nitriding uses anhydrous ammonia (NH
3
) as the nitrogen
source, which has a given ratio of 1:3 (one part nitrogen to three
parts hydrogen). The limitation of the fixed ratio is that the y g )
ammonia will produce a mixed phase compound zone of both
and (usually around 50% each). High internal stresses result
from the different phase volumes, which means that the crystal p , y
interfaces (between and & between and diffusion-zone) are
inherently weak. The thicker the compound zone, the weaker it
becomes, causing weak crystal boundaries within the zone to fail beco es, caus g ea c ys a bou da es e o e o a
even under small loads.
The thinner the compound zone, the more ductile the steel and
the better its fatigue properties. Ion nitriding allows control of the
thickness of the compound zone.
Gaseous Nitriding
In the diffusion zone
Widely used temperature-range for Gaseous Nitriding of Fe-based alloys: 500 590 C
strong affinity
between Cr and N Cr and N;
formation of
In the diffusion zone
between Cr and N Cr and N;
V and N V and N
Al and N Al and N
element nitride
Also, note that:
- AlN can has other crystal y
structures, like Zn-blend
(ZnS) structure or NaCl
(f.c.c.) structure.
- Apart from TiN, Ti
2
N nitride
can also form can also form.
- Apart from CrN, Cr
2
N
nitride can also form.
FIGURE: Effect of alloying elements on hardness after nitriding. In steels
containing several alloying elements, higher hardness values are
obtainable than if alloying elements are used separately. (Base alloy: 0.35%
C, 0.30% Si, 0.70% Mn).
Pure iron and low-alloy steels will nitride. However, they will exhibit
Nitriding Steels
maximum hardness values of about 35 HRC (by gas nitriding). In the
early days of process development, there was development of the
Nitralloy group of special alloy steels that produce high hardness
l ft it idi Th Nit ll t l t i ll i l t h values after nitriding. The Nitralloy steels contain alloying elements such
as chromium, molybdenum, vanadium, tungsten, and aluminum.
The high hardness values achieved in the Nitralloy steels are due to The high hardness values achieved in the Nitralloy steels are due to
the affinity of the alloying elements to form stable nitrides at designated
process temperatures. The resulting hardness value is a function of the
amount of these elements present. Considerably higher hardness p y g
values are exhibited with steels containing up to approximately 1 to 3%
Al. Above 3%, there is no effect on hardness. Generally the maximum
amount of aluminum permitted in the steel is in the region of 1.5%.
Above 1% Al will lead to surface cracking under extreme surface load
conditions.
Although this discussion has centered on the Nitralloy steels steels that Although this discussion has centered on the Nitralloy steels, steels that
contain the same elements either individually or collectively will nitride.
This includes stainless steels, tool steels, and alloy steels.
Nitriding Steels
S l ti f hi h it id t t th i k f i
Issue of nitride-networking at the corner
Selection of higher nitridng temperatures poses the risk of grain-
boundary networking with iron nitrides at the periphery of the grain
boundaries, leading to premature component failure at sharp corners.
FIGURE: A sharp corner profile,
ill t ti th ff t f it
FIGURE: Micrographs of white nitride
layers developed on AMS 6470 steel.
White layer 0.033 mm thick formed after
illustrating the effects of nitrogen
enrichment (nitride networking) at
the corner.
y
single-stage nitriding at 525 C for 60 h.
Buildup of white layer at corner was
0.084 mm.
The corner effect is a phenomenon that can occur in any type of diffusion
Issue of nitride-networking at the corner
e co e e ect s a p e o e o t at ca occu a y type o d us o
heat treatment process, including plasma nitriding, gas nitriding, and
carburizing.
Because nitrogen is diffusing from all angles of the corner a normal Because nitrogen is diffusing from all angles of the corner, a normal
reaction of nitrogen saturation occurs at the corner (particularly on gear
teeth). If allowed to proceed unchecked, a supersaturated solution of
nitrogen can form at the corners, leading to nitride networking throughout nitrogen can form at the corners, leading to nitride networking throughout
the corner region. The net result is that the corner can become very brittle
and prematurely fail by chipping or spalling.
Reduction of the Compound Zone by
the Two-Stage (or Double-Stage) Process
The purpose of the two-stage process is to reduce the thickness of the compound
zone on the immediate surface of the steel by reducing the nitriding potential at an
elevated temperature. The first stage of the process ensures rapid formation of the
white layer and the second stage arrests the formation of the white layer without white layer, and the second stage arrests the formation of the white layer without
allowing the diffusion zone to be denitrided.
The two-stage nitriding process is a relatively simple procedure: Nitriding is carried
out using ammonia gas with a dissociation of approximately 30% at 495 C. This is g g pp y
followed by raising the temperature during the last third of the cycle to 565 C with
a dissociation rate of 75 to 80%.
2 3
H
2
3
] N [ NH +
75%
2
2 / 3
NH
n
3
p
p
r =
H
2
p
> Nitriding depth versus nitriding potential:
Gaseous Nitriding
Example:
Fe-7wt.%Cr alloy nitrided at 580 C and r
n
= 0.03 0.82 atm
-1/2
for 4 h
t
c
D c 2
depth) (nitriding
Cr
N
S
N 2

=

S
N

c
At constant temperature: r
N
nitriding depth = 315.8 (r
N
)

Ref: S.S. Hosmani, R.E. Schacherl and E.J. Mittemeijer: Mater Scie Techn 21, 113 (2005)
About Resistance to Oxidation
Compared to steels that have undergone traditional case hardening
t h i it id d t l ff i d i d id ti techniques, nitrided steels offer improved corrosion and oxidation
resistance.
The nitrided surface of an alloy steel or tool exhibits increased resistance The nitrided surface of an alloy steel or tool exhibits increased resistance
to saltwater corrosion, moisture, and water.
However, this does not apply to stainless steels; in fact, their resistance However, this does not apply to stainless steels; in fact, their resistance
to corrosion will be reduced. This is because chromium has an affinity for
oxygen, readily forming chrome oxide on the stainless steel surface. The
chrome oxide acts as a barrier to nitriding. For diffusion to occur, the g
surface must be passivated, thus reducing corrosion resistance.
How can we maintain the stainless/corrosion How can we maintain the stainless/corrosion
property of steel without compromising surface-
mechanical properties ? mechanical properties ?
Possible Answer: Low-temperature surface alloying of steels
-- Low Low--temperature Carburization of Stainless temperature Carburization of Stainless--Steels Steels
Conventional gas carburization of stainless steels is
> Scientific Background
g
performed at up to 1010 C.
Hardness values can be increased from ~200 HV to between
700 and 750 HV.
The resulting microstructures contain chromium carbides
This affects corrosion property.
Refs.: f
Y. Cao, F. Ernst, G.M. Michal: Acta Materialia 51, 4171 (2003).
G. M. Michal, F. Ernst, H. Kahn, Y. Cao, F. Oba, N. Agarwal, A.H. Heuer: Acta Materialia 54, 1597 (2006).
-- Low Low--temperature Carburization of Stainless temperature Carburization of Stainless--Steels Steels
The precipitation of chromium carbides requires diffusion of
> Scientific Background
p p q
substitutional elements.
Substitutional element diffusion can be many orders of
magnitude slower than interstitial diffusion.
A processing temperature window exists where significant
carburization depths can be achieved while kinetically
suppressing carbide formation.
Refs.: f
Y. Cao, F. Ernst, G.M. Michal: Acta Materialia 51, 4171 (2003).
G. M. Michal, F. Ernst, H. Kahn, Y. Cao, F. Oba, N. Agarwal, A.H. Heuer: Acta Materialia 54, 1597 (2006).
-- Low Low--temperature Carburization of Stainless temperature Carburization of Stainless--Steels Steels
> Scientific Background
Conventional
carburization:
900 ~ 1000 C 900 ~ 1000 C
Low temperature
Carburization
Diagram for two austenitic stainless steels with different carbon concentrations
-- Low Low--temperature Carburization of Stainless temperature Carburization of Stainless--Steels Steels
> Past work by the research-groups in the USA resulted in
following conclusions
Low temperature carburization can produce carbon
concentration > 10 at. % in 316 stainless steel while
maintaining single phase austenite maintaining single phase austenite.
As a result of LTCSS treatment hardness levels approaching
1200HV, surface compressive residual stress values of ~2.1
GPa and enhanced corrosion resistance are achieved.
Refs.:
Y.Cao,F.Ernst,G.M.Michal:Acta Materialia 51(2003)4171.
G.M.Michal,F.Ernst,H.Kahn,Y.Cao,F.Oba,N.Agarwal,A.H.Heuer:ActaMaterialia54(2006)1597.
etc....
surface
schematic: c/s of surface hardened specimen
Core
Hardened Layer Core
(ferritic region)
e
S
u
r
f
a
c
e
Figure: SEM image of low temperature
carburized 316 Stainless Steel.
Figure: Optical image of nitrided
Fe-1Cr alloy.
Ref.: S.S. Hosmani, et. al., J. Mat. Sci. 43 (2008) 2618. Ref.: Y. Cao, et. al.: Acta Materialia 51 (2003) 4171.
Nitrocarburizingg
Nitrocarburizing
In nitrocarburizing, an ammonia atmosphere is blended with carbon- and-
oxygen-containing gases that are usually based on carbon dioxide or
allow carbon dioxide to be generated Ammonia is considered to be the allow carbon dioxide to be generated. Ammonia is considered to be the
most readily and actively available source of nitrogen for the process and
is blended with the other process gas supplies of carbon (from a
hydrocarbon gas, e.g. LPG-gas) and oxygen from other sources. hydrocarbon gas, e.g. LPG gas) and oxygen from other sources.
As in gas nitriding, the cracked nascent ammonia gas will dissociate at
the steel surface and react with the hydrocarbon gas to form both y g
nascent nitrogen and free carbon.
In accordance with the homogeneous water gas reaction, carbon dioxide
reacts under near-equilibrium conditions with the hydrogen generated
according to the reaction:
CO
2
+ H
2
H
2
O + CO
If we assume that ammonia is supplied at a constant pressure to the
Nitrocarburizing
e assu e t at a o a s supp ed at a co sta t p essu e to t e
process, a drop in the partial pressure of hydrogen will occur due to the
above reaction. This in turn will increase the nitriding potential of the
process and lead to:
NH
3
+ CO HCN + H
2
O
This means that some hydrogen cyanide (HCN) gas will form as a
HCN N() + C() + (1/2)H
2
This means that some hydrogen cyanide (HCN) gas will form as a
byproduct of the process. The hydrogen cyanide will contribute both
nitrogen and carbon to the process reaction, thus improving the
nitriding potential of the total process gas. nitriding potential of the total process gas.
In above reaction of HCN, carbon too diffuses into the steel. Car bon,
moreover, diffuses into the steel via the Boudouard reaction (CO C +
CO ) and the heterogeneous water gas reaction CO
2
) and the heterogeneous water gas reaction.
The interrelationship between nitriding potential, carburizing potential,
Nitrocarburizing
e te e at o s p bet ee t d g pote t a , ca bu g pote t a ,
and the nitrocarburized microstructures is shown in the Figure below. By
means of this Figure, it is possible to assess the gas composition that
has to be established and maintained for a specific microstructure at a
given temperature.
At about 570 C
FIGURE: Influence of the gas composition on nitride formation in the
compound layer.
The metallurgical results of the process are very similar to the classical
Nitrocarburizing
The metallurgical results of the process are very similar to the classical
nitriding process, with the exception that now there is carbon in the layer.
The addition of gases that release CO
2
at nitriding temperature to the
original nitriding atmosphere consisting of NH
3
enhances the nitriding
effect of a nitrocarburizing atmosphere because of the increased nitriding
characteristic and the transformation of nitrogen from the decomposition
f HCN I h t h t th l it b i i of HCN. In such atmospheres, at the usual nitrocarburizing
temperature of about 570 C for ferrous materials, processing times
of 24 h are enough to lead to the formation of nitrocarburized
microstructures consisting of a compound layer and a diffusion zone microstructures, consisting of a compound layer and a diffusion zone,
whose properties are such as to greatly enhance the component
behavior under many loading conditions.
Above all the economic advantage of a considerably shorter
processing time and an easier solution to the problem of waste
management than in salt bath nitrocarburizing have made gas
nitrocarburizing as the most often used process with ferrous materials to
date.
Nitrocarburizing
One of the main objective of the ferritic nitrocarburizing process is to
form nitrides and, most importantly, surface carbon, which will
encourage the -nitride phase in the surface of the steel. The surface encourage the nitride phase in the surface of the steel. The surface
carbon comes from three sources:
Decomposition of the process gas
Steel chemistry
Hydrocarbon additive gas
Nitrocarburizing
Most gear manufacturing depends on control tolerance and precision
treating in terms of distortion. This means that a process that can offer
a significant reduction in distortion and an improvement in gear a significant reduction in distortion and an improvement in gear
performance will be closely scrutinized. Ferritic nitrocarburizing is
performed at a low temperature (in the ferrite region) and introduces
both carbon and nitrogen into the surface of the steel, followed by a
quench to improve fatigue resistance with a minimal amount of
distortion. Gear manufacturers are finding that the process can be
applied to gear cutting hobs, cutting tools, and broaching tools. The
process also improves wear properties and compression stress at
the gear surface.
Th k bl ti f d l ll t l b
Nitrocarburizing
The remarkable properties conferred on low-alloy steels by
nitrocarburizing have been highlighted comprehensively in the
literature in the past few years. In addition to enhanced fatigue
resistance the increase in wear resistance attributed to the formation resistance, the increase in wear resistance, attributed to the formation
of a thin compound layer composed of the single-phase -nitride or
carbonitride, has been shown to be dramatic. Typically, a compound
layer of some 12 to 20 m has been reported as a result of a layer of some 12 to 20 m has been reported as a result of a
conventional 3 h nitrocarburizing treatment at a temperature of 570 C.
FIGURE: Typical compound FIGURE: Typical compound
layer on nitrocarburized mild
steel
It has been suggested recently that the properties obtained by the 60/80
Nitrocarburizing
t as bee suggested ece t y t at t e p ope t es obta ed by t e 60/80
h gaseous nitriding of classical nitriding steels can be matched by a
12/20 h nitrocarburizing treatment. In this context, an added advantage
of nitrocarburizing would be the replacement of the brittle duplex white
layer, characteristic of gaseous nitriding, by the more ductile single-
phase compound layer.
FIGURE: Comparative hardness profiles produced by 80 h nitriding
and 16 h nitrocarburizing.
Oxynitriding Oxynitriding
Oxynitriding
The oxynitriding process has grown in popularity over the past two
decades, especially in pulsed plasma nitride processing.
The purpose of the oxynitriding process is to form a controlled oxide The purpose of the oxynitriding process is to form a controlled oxide
layer on the surface of the treated steel. Once the oxide barrier has
been formed, there is a resistance to corrosion. The degree of
corrosion resistance will be determined by the thickness of the oxide y
layer, which in turn is determined by both time and temperature. The
oxynitriding process can be performed in gas, salt, or plasma.
The procedure is done on completion of the nitride cycle when the The procedure is done on completion of the nitride cycle, when the
control program moves into the cooldown mode. It is during the
cooldown procedure that oxygen is fed into the process chamber.
Th id ti l i ll d 1 thi k b t b i d The oxidation layer is usually around 1 m thick, but can be varied
according to the cooldown time and the time held at an elevated
temperature (around 480 C). Generally the procedure is simple and
adds no significant time to the overall process adds no significant time to the overall process.
Oxynitriding produces a pleasing cosmetic appearance and ensures a Oxynitriding produces a pleasing cosmetic appearance and ensures a
high degree of surface protection against corrosion. The procedure can
be applied to items such as boring bars, cutting tool holders, broaches,
drill bits and cutting tools In fact oxynitriding can be applied to any drill bits, and cutting tools. In fact, oxynitriding can be applied to any
workpiece subject to corrosive conditions and is not restricted to cutting
tool applications.
Examples of oxynitrided piston rods:
Center rod: before treatment.
Two rods at left: untreated and subjected to salt spray testing Two rods at left: untreated and subjected to salt spray testing.
Two rods at right: treated, then subjected to salt spray testing.
Material is similar to H41 400 chromium-molybdenum steels.
The surface finish of the steel after the procedure is dark blue,
almost matte black.
Ferritic Oxynitrocarburizing
This process is simply an addendum at the end of the ferritic nitrocarburizing
procedure. Oxynitrocarburizing involves introducing oxygenin the form of
steam, oxygen, or nitrous oxidein a controlled manner into the process
chamber chamber.
Milling cutter after ferritic
oxynitrocarburizing