Nitriding
Nitriding
NITRIDING
Nitriding is a ferritic
thermochemical method of
1. Cinderella process diffusing nascent or atomic
2. Interstitial diffusion process - solubility of nitrogen in iron nitrogen (Ammonia was
3. stabilizing process by providing an additional temper to the processed steel decomposed, or “cracked,” by heat
to liberate the nascent nitrogen)
4. Adolph Machlet got patent in 1908 into the surface (ferrite phase) of
5. Adolph Fry’s got patent in 1922 steels and cast irons and
6. Wehnheldt and Berghaus got patent for ion nitriding in 1932 precipitating nitrides by holding.
The chapters in this book address many important questions related to the nitriding process:
• Of the many nitriding methods, which one is for you? There are many different and valid reasons for choosing each
relevant nitriding process technique, be it the reduction in thickness of the compound zone, the elimination of the
compound zone, deep case formation, shallow case formation, high wear resistance, or corrosion resistance.
• Of the many different nitridable steels that can be chosen to manufacture the component in question, which one
should be chosen?
• What hardness should the steel have prior to nitriding?
• How much surface stock should be removed prior to nitriding, and what problems are caused if the appropriate amount
of stock is not removed?
• Which furnace should be used? Nitriding Techniques
• How should the process be controlled? Material selection
• How should the steel be prepared? Heat Treater Equipment
• How should the steel be handled after nitriding? Metallurgist Control
Design Testing
Engineer Evaluation
Trouble shooting
An Introduction to Nitriding
1. No phase change like carburising
2. No change to core properties Linear
3. No dimensional change measurement
4. Volumetric change occurs - nitrogen diffusion
5. Chemical composition changes at the surface
Measurement of
capacity
5. Chromium, molybdenum (improves ductility), aluminum(greater affinity towards N, So, good results),
vanadium, and tungsten form fine dispersed stable nitrides
6. Below Ac1 Temperature – Temperature at which austenite begins to form during heating
7. Nitriding Layer = Compound layer + Diffusion layer
8. Nitrided carbon steels have a surface hardness of 300-400 HV and alloyed steels from 700 HV to more
than 1000 HV
9. Nitriding layer = depth to which nascent N has been diffused
11 wt%
5.7 wt%
0.1 wt%
Max.
5.9 wt%
1
Metallurgical Considerations and
Process Requirements
1. Solubility of nitrogen is temperature dependent
5.7 ~ 6.1 % N at 450 °C
Higher process temperatures increased the risk of forming nitride networks, particularly at
corners, due to the higher solubility of nitrogen in iron. When present, nitride networks cause
premature failure at the steel surface by cracking, spalling and exfoliation
Case : 2
Process temp. ∞ Case depth (diffusion rate will be more)
∞ 1/Surface hardness
∞ White layer
Case : 3
The steel to be nitrided should clearly be free of surface decarburization prior to nitriding ;
otherwise, the nitrided surface will exfoliate and peel away from the substrate.
Case : 4
Nickel was not a nitride-forming element, but that it tended to retard the nascent nitrogen
diffusion if present in significant quantities
Case : 5
At high temperatures, anhydrous liquid (no water) ammonia becomes metastable and dissociates
2NH3 ↔ 2N + 3H2
Case : 6
An economical temperature is one that produces an optimum case depth while not adversely
affecting the core properties of the treated steel
Case : 7
Corrosion resistance of nitride layers increases in the order
ε-carbonitride > ε-nitride > γ′-nitride
and can be improved by post-oxidation
Case : 8
If surface not cleaned properly, it causes cracks and corrosion
Case : 9
Incorrect mounting and long polishing with soft cloths results in rounded edges and rounded
edges lead to incorrect thickness measurements
Case : 10
The size and shape of porous zones can be seen in un-etched conditions
Case : 11
The main problems when preparing nitrided layers are rounded edges and cracking or
chipping of the layer during grinding and polishing. By carefully wrapping the sample in a thin
copper foil before hot compression mounting, this problem can be overcome.
Case : 12
For a good nitride case a very good base material is essential. Cracks, inclusions, banding or
deformation of the initial surface decisively influence the quality of the nitrided layer.
Therefore it is also important to evaluate the structure of the base material.
Case : 13
The tempering temperature must be high enough to guarantee structural stability at the
nitriding temperature
Case : 14
Case : 15
Process temp. ∞ Case depth (diffusion rate will be more)
∞ 1/Surface hardness (after certain extent)
∞ White layer
Case : 16
Gas flow ∞ 1/Gas pressure ∞ dissociation rate ∞ 1/Case depth ∞ 1/White layer
Single stage nitriding :
Process technique to reduce the white layer thickness known as the Floe process, or the two-stage process
Stage: 2 Normal nitriding cycle (external ammonia dissociator is necessary for obtaining the required higher second-stage
dissociation)
Harris formula :
Compound zone thickness = √t × f To summarize, the use of a higher temperature during the second
t is process time stage:
f is factor
• Lowers the case hardness
Case depth = K√t • Increases the case depth
case depth is in inches • May lower the core hardness depending on the prior tempering
t is in hours temperature and the total nitriding cycle time
K is factor • May lower the apparent effective case depth because of the loss
of core hardness, depending on how effective case depth is defined
STAGES
PRE-CLEANING
7. Product specifications
8. Process parameters
9. Accurate control of process parameters
Typically, three reactions take place at the steel surface when the steel is at the set process temperature:
NOTE :
When the nitrogen concentration exceeds the nitrogen solubility limitation of α-Fe (ferrite), the first phase developing at the
surface of the ferrous substrate is γ′. Then ε phase is formed with increasing of the nitrogen concentration.
NOTE :
For preventing rounded edges , use copper foil & nickel foil to cover the specimen before hot mounting
OPTICAL MICRO-GRAPH :
γ′ = Dark grey
ε = Light grey
Process steps in Gas Nitriding
1. Prior heat treatment condition :
For wear, corrosion resistance and fatigue endurance → Hardened & tempered condition
For wear, corrosion resistance → Annealed / Normalised condition
For cast irons → Annealed condition
Stress relieving and tempering temperatures should be 20-30°C above the nitriding temperatures, otherwise distortion will happen
2. Pre- cleaning :
One method consists of vapor degreasing parts and then abrasive cleaning them with aluminum oxide grit or other abrasives such as
garnet, or silicon carbide, immediately prior to nitriding. Any residual grit must be brushed off before parts are loaded into the furnace.
Parts should be handled with clean gloves.
A second method consists of pre-oxidizing the parts in an air atmosphere at approximately 330 °C (625 °F). This may be done as a
separate operation, or it may be incorporated as part of the heating portion of the nitriding cycle if suitable precautions are taken.
Stress relieving and tempering temperatures should be 20-30°C above the nitriding temperatures, otherwise distortion will happen
NOTE :
Ammonia and oxygen form an explosive mixture within a certain concentration range, so nitrogen purging has to be done in the
chamber
3. Purging :
Nitrogen versus Ammonia for Purging. Advantages of nitrogen as a purging gas include its safety,
ease of handling, and ease of control. The use of nitrogen, however, requires additional equipment,
including piping.
Ammonia requires no additional equipment and is relatively safe when properly handled; Caution:
mixtures of 15 to 25% ammonia in air, however, are explosive if ignited by a spark.
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Microstructures of Nitrided Iron and
Steel
Why white layer is white in color
Because ε & γ′ phase are not attacked by alcoholic nitric acid etching