PRE-FACE :

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

Control on Successful Process Process

Process Parameters
Parameters
 An Introduction to Nitriding
The following steels can be gas nitrided for specific applications:

• Aluminum-containing low-alloy steels (Table 1)

• Medium-carbon, chromium-containing low-alloy steels of the 4100, 4300, 5100, 6100, 8600, 8700, and 9800
series
• Hot-work die steels containing 5% chromium such as H11, H12, and H13
• Low-carbon, chromium-containing low-alloy steels of the 3300, 8600, and 9300 series
• Air-hardening tool steels such as A-2, A-6, D-2, D-3, and S-7
• High-speed tool steels such as M-2 and M-4
• Nitronic stainless steels such as 30, 40, 50, and 60
• Ferritic and martensitic stainless steels of the 400 and 500 series
• Austenitic stainless steels of the 200 and 300 series
• Precipitation-hardening stainless steels such as 13-8 PH, 15-5 PH, 17-4 PH, 17-7 PH, A-286, AM350, and
AM355
 An Introduction to Nitriding
7.71 wt%

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

2. Carbon content ∞ ε phase

∞ 1/ γ′ phase

3. Alloy content ↓ Diffusion rate of N ↑

Alloy content ↑ Diffusion rate of N ↓

4. Phases → ε (epsilon) phase → 450 °C → Hexagonal → Fe2-3N

→ γ′ ( gamma prime) phase → 490 °C → FCC → Fe4N
→ ζ (zeta) phase → ≥500 °C → Orthorhombic → Fe2N (not used in nitriding practice)

Process control factors :

• Total surface area to be nitrided

• Process pressure inside the sealed process chamber
• Gas delivery pressure system into the sealed process chamber
• Exhaust gas system from the sealed process chamber
• Control of the preheat treatment procedure prior to nitriding, including stress relief and prehardening and tempering
• Quality and integrity of the steel surface precleaning prior to nitriding
• Consistent steel chemistry to maximize “nitridability”
 Saturated solution of N in
immediate surface of the
Case : 1 formed case

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

Nitrogen Potential ∞ Case depth

∞ White layer

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 :

Done in 500 °C – (15~30%) dissociation of ammonia – (70~85% ammonia) in atmosphere

Double stage nitriding (FLOE PROCESS) :

Process technique to reduce the white layer thickness known as the Floe process, or the two-stage process

Stage: 1 Normal single stage nitriding cycle

500 ~ 525 °C – (15~30%) dissociation of ammonia – (70~85% ammonia) in atmosphere

Stage: 2 Normal nitriding cycle (external ammonia dissociator is necessary for obtaining the required higher second-stage
dissociation)

525 ~ 595°C – (65~80%) dissociation of ammonia – (15~25% ammonia) in atmosphere

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

PREVENTS EXPLOSION FURNACE PURGING CYCLE @ 150 °C PREVENTS OXIDATION

EXPLOSION HAZARD @ 330 °C

Dilution of the ammonia lessens

the discomfort to employees
working near the furnace. The
introduction of nitrogen into the
retort can be delayed until the
nitrided parts have cooled to
below 149 °C (300 °F).
PROCESS PARAMETERS :

1. Nitriding Potential - Thermodynamics

2. Temperature - Thermodynamics
3. Time - Kinetics
4. Chemistry
5. Pressure
6. Ammonia dissociation rate ( measured by using a burette in the furnace exhaust gas )

SUCESSFUL GAS NITRIDING PROCESS :

7. Product specifications
8. Process parameters
9. Accurate control of process parameters

Inlet gas = NH3

Outlet gas = NH3 + N2 + H2

Typically, three reactions take place at the steel surface when the steel is at the set process temperature:

1. NH3 →3H + Nad (dissociation)

2. Nad →[N] (dissolution)
3. Nad + Nad →N2 (Formation of inert gas)
Microstructures of Nitrided Iron and
Steel
1. Compound (white) layer → multiphase compound containing ε & γ′ phases
→ does not diffuse into the steel, but remains on the immediate surface
→ can be removed by blasting
∞ time
∞ temperature
∞ gas composition Compound (white) layer → Wear, Corrosion resistance
Diffusion layer → fatigue endurance

2. Diffusion layer → interstitial solid solution of N in iron

3. Transition layer
4. Material core

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.

If not performed → Uneven compound zone will form

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

Why nitrided layer is dark in color

Because nitriding needles and other phases are attacked by alcoholic nitric acid etching
 Infiltration & Permeation Process
• Infiltration (event) is the process by which N on the surface enters the material. ... Infiltration rate is a
measure of the rate at which a particular material is able to absorb N. It is measured in millimeters per
hour. The rate decreases as the material becomes saturated.
• Permeate = N
• permeation  (material property) is the penetration of a permeate