Lecture 27: Nitriding

Nitriding is a heat treatment process used to improve the surface hardness, wear resistance,
and fatigue strength of steel and other ferrous alloys by introducing nitrogen into the
material's surface

Types of Nitriding Processes

In nitriding, hydrogen does not significantly diffuse into steel because:

• Low Solubility in Steel – Hydrogen has very low solubility in steel at nitriding
temperatures (typically 500-600°C).

• Partial Pressure and Diffusion Mechanics – Hydrogen molecules have a high

diffusion rate in gases and escape quickly from the nitriding environment rather than
penetrating the metal.
Bath consist of NaCN, KCN, Na2CO3, NaCl etc
 Nitriding vs. Carburizing
Nitriding carburizing

Process Introduces nitrogen into the steel Introduces carbon into the steel
surface. surface
Working Temperature 500–600°C (lower temperature). 850–950°C (higher temperature).

Hardness Up to 1200 HV Around 700–900 HV

(very high surface hardness). (lower than nitriding).
Quenching self-hardening process due to requires quenching and tempering.
nitride formation.
Distortion Minimal, as no quenching is Higher distortion due to
required. quenching.
Depth of Hardening 0.1–0.7 mm (shallow case depth) 0.5–3 mm (deeper case depth).

Process Time Long (10–100 hours). Shorter (a few hours).

Suitable Materials Low-alloy steels, nitriding steels, Low-carbon steels, low-alloy
tool steels. steels.
 Surface hardening

Principle: hardening being by extremely rapid heating and quenching of wearing surfaces which has no effect on
the interior core.

Induction hardening

• Induction hardening is a surface hardening technique that uses electromagnetic induction to rapidly heat
specific areas of a metal part, followed by rapid cooling (quenching), resulting in a hardened, wear-
resistant surface

How it works:

• A copper coil carrying a high-frequency alternating

current is placed near the metal part (not touching it).

• The alternating current induces eddy currents and

hysteresis losses within the metal, generating heat
primarily at the surface.

• The part is heated quickly to a temperature above the

transformation range, followed by immediate
quenching (usually with water or oil).

• The rapid cooling causes a martensitic

transformation, which significantly increases the
surface hardness and wear resistance

Applications: bearing areas of crank shaft, cam shaft,

axial shaft etc.,
Flame hardening

• Surface hardening process in which heat (within range of austenising temperature) is applied by a high
temperature flame (oxyacetylene torch) followed by quenching jets of water.

• Steels most suited have carbon content within the range 0.40-0.55%. It is usually applied to medium to large size
components such as large gears, sprockets, slide ways of machine tools, bearing surfaces of shafts and axles, etc.
 Laser hardening

Laser hardening is a surface heat treatment

process that uses a high-energy laser beam to
rapidly heat the surface of a metal (typically
steel) above its austenitizing temperature,
followed by self-quenching due to the rapid
heat dissipation into the cooler underlying
material. This results in a hardened surface
layer with improved wear and fatigue
resistance
Comparison between surface hardening and case hardening processes
 Stainless Steels

Stainless steel is any one of the steel alloys that contains at least 10.5% chromium in
the admixture of elements (Ni, Mo or Ti).
Austenitic Stainless Steels

Austenitic stainless steels are primarily composed of:

• Chromium (Cr) (16–26%) – Provides corrosion resistance
• Nickel (Ni) (6–35%) – Enhances toughness and stabilizes austenite phase
• Manganese (Mn) (up to 10%) – Can be used as an alternative to nickel in some grades

Characteristics
• Non-magnetic in annealed condition (can become slightly magnetic when cold-worked)
• High corrosion resistance (especially to oxidation and acids)
• Excellent toughness and ductility even at cryogenic temperatures
• Good weldability and formability
• Cannot be hardened by heat treatment, only by cold working

Examples: 304, 316, 321, 310 grades

Heat Treatment
• Solution Annealing (1050-1150°C, then rapid cooling in water/air): removes work hardening
• Stress Relieving (650-750°C, followed by slow cooling): Reduces residual stresses from welding
or cold working
• Problem: Sensitization (450-850°C): Can cause chromium carbide precipitation, leading to
intergranular corrosion

This precipitation leads to a chromium-depleted zone around the grain boundaries, making the
steel vulnerable to corrosion in certain environments
Weld decay
Weld decay is a corrosion process that mainly occurs because of sensitization (regions susceptible to
corrosion) in the heat affected Zones (HAZ) of metal during welding operations

Methods for preventing weld decay and sensitization include:

• Using low carbon grade stainless steels

• Use alloy with stabilized grades of titanium or niobium, which are strong carbide formers.

Sensitization and weld decay both are forms of intergranular corrosion

Ferritic Stainless Steels

Ferritic stainless steels are primarily composed of:

• Chromium (Cr) (10.5–30%) – Provides corrosion resistance
• Carbon (C) (≤ 0.1%) – Low carbon content to improve ductility and weldability
• Molybdenum (Mo) (0–4%) – Enhances corrosion and pitting resistance

Characteristics
• Magnetic due to the body-centered cubic (BCC) structure
• Good corrosion resistance, especially to stress corrosion cracking
• Moderate strength and ductility, lower than austenitic stainless steels
• Good oxidation resistance, especially at high temperatures
• Poor weldability, prone to grain growth and embrittlement in heat-affected zones
• Cannot be hardened by heat treatment, only by cold working

Common grades : 430, 409, 439, 446 grades

Heat Treatment
• Annealing (750-850°C, followed by slow cooling): Improves ductility and relieves stresses
• Stress Relieving (200-400°C, slow cooling): Reduces internal stresses from forming or welding
• No hardening by heat treatment (hardened only by cold working)
• Rarely shows sensitization

Ferritic stainless steels typically have a low carbon content (less than 0.20%). This low carbon content
limits the formation of chromium carbides (Cr23C6) at grain boundaries, which are the primary culprits in
intergranular corrosion
Martensitic Stainless Steels

Martensitic stainless steels have a unique composition that allows them to be heat-treated for high
strength and hardness:
• Chromium (Cr) (10.5–18%) – Provides corrosion and oxidation resistance
• Carbon (C) (0.1–1.2%) – Higher carbon content enables hardening through heat treatment

Characteristics
• Magnetic due to its body-centered tetragonal (BCT) crystal structure
• High strength and hardness after heat treatment
• Moderate corrosion resistance (lower than austenitic and ferritic stainless steels)
• Good wear resistance
• Poor weldability due to high carbon content, requiring preheating and post-weld treatment
• Brittle in hardened state, but improved toughness with tempering

Example: AISI 410, AISI 420, AISI 440, AISI 431

Heat Treatment
1. Hardening (950-1050°C, quenching in oil or air): forms hard martensitic structure
2. Tempering (200-700°C, air cooling): Adjusts hardness and toughness
3. Annealing (750-850°C, slow cooling in furnace): Softens material for machining and forming
Duplex Stainless Steels
Composition
• Chromium (Cr) (18–30%) – Provides corrosion and oxidation
resistance
• Nickel (Ni) (4–8%) – Stabilizes the austenitic phase, improving
toughness
• Molybdenum (Mo) (0–5%) – Enhances corrosion resistance,
particularly to pitting
• Nitrogen (N) (0.1–0.3%) – Increases strength and corrosion
resistance
• Manganese (Mn) (0.5–2%) – Can partially replace nickel to
stabilize austenite

Characteristics
• High strength, nearly twice as strong as austenitic stainless steels
• Good corrosion resistance, especially to stress corrosion cracking (SCC) and pitting
• Good toughness, though slightly lower than austenitic grades
• Magnetic, due to the ferritic phase
• Lower thermal expansion, reducing distortion in high-temperature applications
Heat Treatment
1. Solution Annealing (1020-1100°C, then rapid cooling in water/air): Restores mechanical
properties and corrosion resistance
2. No hardening by heat treatment (hardened only by work hardening)
3. Avoid prolonged exposure to 300-500°C to prevent embrittlement

Common grades : 2205, 2507 grades

Precipitation hardenable Stainless Steels
Precipitation-hardening stainless steels contain elements that form fine precipitates during heat treatment,
increasing hardness and strength. The typical composition includes:
• Chromium (Cr) (12–18%) – Provides corrosion resistance
• Nickel (Ni) (4–9%) – Enhances toughness and stabilizes the austenitic phase
• Copper (Cu) (0.5–5%) – Contributes to precipitation hardening
• Aluminium (Al) (0.1–1.5%) – Forms strengthening precipitates
• Titanium (Ti) or Niobium (Nb) (0.2–1%) – Improves strength and corrosion resistance
• Molybdenum (Mo) (0–2%) – Enhances corrosion and pitting resistance
 Characteristics
• High strength and hardness, comparable to martensitic stainless steels
• Good corrosion resistance, like austenitic stainless steels
• Excellent mechanical properties, even at high temperatures
• Can be heat-treated to various strength levels
• Magnetic or non-magnetic, depending on the microstructure

Common grades : 17-4 PH, 15-5 PH, 13-8 PH

Heat Treatment
• Solution Treatment (1020-1060°C, then rapid cooling: Dissolves precipitates and retains ductility
• Aging (480-620°C for 1-4 hours, then air cooling): Forms fine precipitates that harden the material
• Various aging conditions (H900, H1025, H1150, etc.): Higher temperatures lead to lower strength but
improved toughness
 Lecture 29: Heat treatment of Tool steels

Tool steel refers to a group of carbon and alloy steels specifically designed and heat-treated to possess high
hardness, wear resistance, and the ability to hold a cutting edge, making them suitable for tools and tooling
applications

Composition: Tool steels are typically high-carbon or alloy

steels
• carbon content ranging from 0.4% to 1.5%
• alloying elements that form carbides in tool steel are:
tungsten, chromium, vanadium and molybdenum
 High Speed Steels

• used in tools for machining with swarf removing at great speed (higher than 30 m/min)
• This process produces heating in the tool during operation, and for that reason the tool must be extra-
hard (63–68 HRC) and keep that hardness at high temperatures (around 600 °C)

Composition:
• the total of Mo, V and W = 7% of materials
• Carbon accounts = 0.6%

Microstructure: consist of a tempered martensitic matrix with

dispersed and refractory carbides

Properties:
➢ The most important property of high-speed steels is the
ability to retain a high hardness at elevated temperatures
➢ high hardness, wear resistance, and hot hardness
 Heat treatment cycle for 18-4-1 tool steel (High speed steel)
18 percent tungsten (W), 4 percent chromium (Cr), 1 percent vanadium (V)

1. Hardening Process:
• Heating process is done at two stages to avoid thermal shock and microcracking of steels
• First stage heated to 850 C for 4-10 mins for uniforming temperature from core to surface
• Second stage heated at 1250-1300 C in salt bath furnace (different furnace) : All carbides will dissolve
except vanadium carbide
• Salt bath heating provides uniform and quick heating to reduce oxidation and decarburisation
2. Soaking: holding time is 1 hour for each 25 mm thick part as per ASTM
3. Quenching:
• Oil quenching gives cooling rate faster than critical cooling rate
• Mf is below room temperature → retained austenite
• Structure at room temperature consists of 60% martensite, 30% retained austenite and 10% alloy
carbides
4. Sub-zero treatment:
• Steel is cooled upto -80 C to convert retained austenite to martensite
• After this, one tempering cycle is must to relieve internal stress formed due to newly formed martensite
• Sub zero treatment reduces the no.of tempering cycles, doesn’t fully convert retained austenite to
martensite.
5. Tempering process-I:
• Hold at constant temp of 550 C for 2 to 2.5 hours followed by oil quench to room temperature.
• Objective to relieve internal stress and brittleness; to convert retained austenite to martensite.
• retained austenite tends to transform into martensite rather than bainite because the tempering
temperature range (typically 400-600°C) is within the temperature range where the kinetics of
martensite formation are favored and the carbon content of the retained austenite is not high enough
to promote bainite formation
• Newly formed martensite during tempering having high order microstress due to that there is more
chances of micro-cracking→ second tempering process
6. Tempering process II
• To relieve microstress due to newly formed martensite
• To further convert some retained austenite to martensite
• Some alloy carbides will separate out

7. Finally retained austenite reduces below 5%