Phase Diagrams in Materials Science

phase diagram is a graphical map showing the phases present in an alloy system at
equilibrium under varying conditions of temperature, pressure, and composition1. For most
metallurgical systems, pressure is held constant, so the diagram plots temperature versus
composition2.

Key Concepts and Definitions

• Component: A chemically distinct element or compound in an alloy (e.g., Fe and C

in steel)3.

Phase: A region within a material that has uniform physical and chemical

• characteristics4. A single-phase system is

homogeneous; a system with multiple phases is heterogeneous5.

• Equilibrium: A state of minimum free energy where the phase characteristics of the
system remain constant over time6.

• Metastable State: A non-equilibrium state that may persist for a very long time,
appearing stable7.

Cementite (Fe3C) is a classic example of a metastable phase8.

 • Solvus Line: The line on a phase diagram that separates a single-phase solid region
from a two-phase solid region, indicating the limit of solid solubility9.

Invariant Reactions

These are reactions where three phases are in equilibrium at a specific temperature and
composition10:

• Eutectic: A liquid phase transforms into a mixture of two different solid phases
upon cooling (LcoolingS1+S2)11.

• Eutectoid: A solid phase transforms into a mixture of two different solid phases
upon cooling (S1coolingS2+S3)12. This is crucial in the Fe-Fe₃C system13.

• Peritectic: A liquid and a solid phase combine to form a new, single solid phase
upon cooling (L+S1coolingS2)14.

Microstructure Development and the Lever Rule

The microstructure of an alloy depends on its composition and the cooling rate15.
 • Lever Rule: In a two-phase region, the lever rule is a mathematical tool used to
calculate the weight percentage of each phase16161616.

• Equilibrium (Slow) Cooling: Allows for complete diffusion, resulting in a uniform

microstructure as predicted by the phase diagram17.

• Non-Equilibrium (Fast) Cooling: Diffusion is too slow to maintain equilibrium. This

results in a non-uniform, layered microstructure called a
cored structure, where the center of a grain is rich in the higher-melting-point
element and the outer layers are rich in the lower-melting-point element18181818. This
cored structure can be eliminated by a high-temperature heat treatment called

homogenization, which allows diffusion to even out the composition19.

The Iron-Iron Carbide (Fe-Fe₃C) Diagram

This diagram is essential for understanding the properties and processing of steels and
cast irons20.

Phases and Their Properties

• α-Ferrite (BCC): A solid solution of carbon in BCC iron. It is soft, ductile, and
magnetic. Max C solubility is 0.022 wt% at 727°C21. It has an approximate tensile
strength of 40,000 psi and 40% elongation22.

• γ-Austenite (FCC): A solid solution of carbon in FCC iron. Denser than ferrite, with a
higher C solubility of up to 2.14 wt% at 1147°C23. It is non-magnetic, tough, and
 forms the basis for most heat treatments24.

• Cementite (Fe3C): A hard, brittle intermetallic compound containing 6.67 wt%

carbon25. It strengthens steel but reduces ductility26.

• Pearlite: The eutectoid microstructure formed from austenite at 727°C, consisting

of alternating lamellae (layers) of soft ferrite and hard cementite27. It has an
approximate tensile strength of 120,000 psi and 20% elongation28.

Microstructure Evolution in Steels

• Eutectoid Steel (0.76% C): Upon slow cooling, austenite transforms completely
into pearlite29.

• Hypoeutectoid Steel (< 0.76% C): As it cools through the α + γ region, proeutectoid
ferrite precipitates from austenite. When the remaining austenite reaches the
eutectoid composition (0.76% C) at 727°C, it transforms into pearlite. The final
microstructure is proeutectoid ferrite plus pearlite30.

• Hypereutectoid Steel (> 0.76% C): As it cools, proeutectoid cementite

precipitates from austenite along grain boundaries. The remaining austenite then
transforms into pearlite at 727°C. The final microstructure is pearlite surrounded by
a network of proeutectoid cementite31.
Heat Treatment of Steels �

Heat treatment involves the controlled heating and cooling of steel to achieve desired
mechanical properties32.

Annealing and Normalizing

• Annealing: A process of heating and slow cooling, typically in a furnace, to produce

a soft and ductile microstructure33. For hypoeutectoid steels, this involves heating
to about 30°C above the A₃ line; for hypereutectoid steels, heating is to about 30°C
above the A₃,₁ line to avoid a coarse cementite network34.

• Normalizing: Heating to about 55°C above the upper critical temperature (A₃ or
Acm), followed by cooling in still air35. The faster cooling rate (compared to
annealing) produces a finer, more abundant pearlite structure, resulting in higher
strength and hardness but lower ductility36363636.

Hardening and Tempering

• Hardening: This process involves heating steel to form austenite and then
quenching (rapidly cooling) it to form martensite37373737. Martensite is a hard, brittle,
supersaturated solid solution of carbon in a body-centered tetragonal (BCT) iron
lattice38. This structure forms because the rapid cooling prevents carbon from
diffusing out of the austenite, trapping it and distorting the crystal lattice39. The
minimum cooling rate required to form 100% martensite is the

critical cooling rate (CCR)40.

 Hardenability is the measure of a steel's ability to be hardened by forming
martensite throughout its cross-section41.

• Tempering: A heat treatment applied to hardened steel to reduce its brittleness and
increase toughness42. The steel is reheated to a temperature below 727°C, held for a
time, and then cooled43. This allows the highly stressed BCT martensite to transform
into a stable structure of fine cementite particles within a ferrite matrix, known as

tempered martensite44. Increasing the tempering temperature decreases hardness

and strength but significantly increases ductility and toughness45.

Surface Hardening (Case Hardening)

These processes produce a hard, wear-resistant surface (case) while maintaining a softer,
tougher core46.

• Carburizing: Carbon is diffused into the surface of low-carbon steel at high

temperatures (~925°C)47474747. A subsequent hardening treatment is required to
make the high-carbon case martensitic and hard, while the core remains tough48.

• Nitriding: Nitrogen is diffused into the surface of alloy steels at lower temperatures
(500-550°C), forming hard iron nitrides49. No quenching is necessary, minimizing
distortion50505050. However, the process is slow and can form a brittle "white layer" on
the surface that may need to be removed51515151.

• Flame & Induction Hardening: These methods do not alter the chemical
composition52. They are used on steels with sufficient carbon (0.3-0.6%) to be
hardenable53. The surface is rapidly heated into the austenite range by an
oxyacetylene flame or a high-frequency magnetic field and then immediately
quenched54545454.