CHAPTER 6

Phase Equilibrium Diagrams

Ehmiel Steve D. Celo
Lucky Ace L. Flores
 PHASE DIAGRAM
• In the simplest sense a phase diagram demarcates regions of existence of
various phases. This is similar to a map which demarcates regions based on
political, geographical, ecological etc. criteria.
→ Phase diagrams are maps
• Phase diagrams are also referred to as “EQUILIBRIUM PHASE DIAGRAMS”.
 Phase
• Physically distinct, chemically homogenous and mechanically separable region of a system.
(e.g. gas, crystal, amorphous...)

• Gases - Gaseous state always a single phase

→ mixed at atomic or molecular level
• Liquids - Liquid solution is a single phase
→ e.g. NaCl in H2O
- Liquid mixture consists of two or more phases
→ e.g. Oil in water (no mixing at the atomic/molecular level)
• Solids - In general due to several compositions and crystals structures many phases are possible
- For the same crystal structure different compositions represent different phases.
→ e.g. in Au-Cu alloy 70%Au-30%Cu & 30%Au-70%Cu are different phases
 ALLOYING SYSTEMS
Alloy is a metal composing of a mixture of elements. Most of alloys are composed of a base
metal with small amounts of additives or alloying elements. The typical examples of alloys are
steel/cast iron (iron base alloys), bronze/brass (copper base alloys), aluminum alloys, nickel
base alloys, magnesium base alloys, titanium alloys.

• Binary system - It means that alloying have two metals only.

• Ternary system - It means that alloying have three metals only.
• Multi system - It means that alloying have three and more than that metals.
 PHASE EQUILIBRIUM DIAGRAMS
(EUTECTIC TYPE)

• The two components are soluble in each other in the liquid state but are completely insoluble
in each other in the solid state. As an example of eutectic are carbon steels .
• The term EUTECTIC means Easy Melting → The alloy of eutectic composition freezes at a
lower temperature than the melting points of the constituent components.
 PHASE EQUILIBRIUM DIAGRAMS
(SOLID SOLUTION TYPE)
• Solid solution is a phase, where two or more elements are completely soluble in each other.
• The solid mentioned is crystalline.
• The solid + liquid region is not a semi-solid (like partly molten wax or silicate glass). It is a
crystal of well defined composition in equilibrium with a liquid of well defined composition.
• A and B components could be pure elements (like in the Ag-Au, Au-Pd, Au-Ni, Ge-Si) or
compounds (like Al2O3-Cr2O3).
Substitution solid solution - If the atoms of the solvent metal and solute element are
of similar sizes (not more, than 15% difference), they form substitution solid solution, where
part of the solvent atoms arc substituted by atoms of the alloying element .
Interstitial solid solution - If the atoms of the alloying elements are considerably
smaller, than the atoms of the matrix metal, , interstitial solid solution forms, where the matrix
solute atoms are located in the spaces between large solvent atoms
 Where:
• C – No. of Components
• P – No. of Phases
• F – No. of degrees of
Freedom
Where F = C – P + 1
• CL - Composition of the
liquid .
• CS - Composition of the
solid.
• - the compositions
are defined with respect to
one of the components
• T - Temperature
 PHASE EQUILIBRIUM DIAGRAMS
(COMBINATION TYPE)

• Many metals and non-metals are neither completely soluble in each other in the solid state nor are they
completely insoluble. Therefore they form a phase equilibrium diagram of the type shown in figure
 Where:
• are terminal solid solutions
• has the same crystal structure as that of
A (Pb)
• has the same crystal structure as B (Sn)
• L – liquid region
• Liquidus - the substance is entirely liquid.
• Solidus - the substance is entirely solid.
• Solvus - separates a homogeneous solid
solution from a field of several phases
• T - Temperature
 IRON-CARBON DIAGRAM
Eutectic
eutectoid
Pearlite and
Cementine

Austenite

Ferrite
Pearlite and
Carbide
Pearlite

Steel Cast iron

• L Liquid solution of carbon in iron.
• Ferrite is known as α solid solution. Maximum concentration of carbon in δ-ferrite is 0.09
% (1493˚C) temperature of the peritectic transformation. The crystal structure of δ-ferrite is
BCC (cubic body centered).
• Austenite interstitial solid solution of carbon in γ-iron. It has FCC (cubic face centered)
crystal structure, permitting high solubility of carbon up to 2.06% at (1147˚C). It dose not
exist below (723˚C) and maximum carbon concentration at this temperature is 0.83 % .
• Cementite iron carbide, intermetallic compound, having fixed composition Fe3C. It is a
hard and brittle substance, influencing on the properties of steel and cast irons.
• Ledeburite is the eutectic mixture of austenite and cementite.
• Pearlite - is the eutectoid mixture containing 0.80 % C and is formed at 723°C on very
slow cooling. It is a very fine platelike or lamellar mixture of ferrite and cementite. The
white ferritic background or matrix contains thin plates of cementite (dark).
• Martensite - a super-saturated solid solution of carbon in ferrite. It is formed when steel is
cooled so rapidly that the change from austenite to pearlite is suppressed.The interstitial
carbon atoms distort the BCC ferrite into a BC-tetragonal structure (BCT).; responsible for
the hardness of quenched steel
Ferrite Pearlite Austentite

Cementite Ledeburite Martensite

 CRITICAL TEMPERATURES
• Upper critical temperature (point) A3 is the temperature, below which ferrite starts
to form as a result of ejection from austenite in the hypoeutectoid alloys.
• Upper critical temperature (point) ACM is the temperature, below which
cementite starts to form as a result of ejection from austenite in the hypereutectoid
alloys.
• Lower critical temperature (point) A1 is the temperature of the austenite-to-
pearlite eutectoid transformation. Below this temperature austenite does not exist.
• Magnetic transformation temperature A2 is the temperature below which a-ferrite
is ferromagnetic .
 PHASE COMPOSITIONS OF THE IRON-
CARBON ALLOYS AT ROOM TEMPERATURE:
• Hypoeutectoid Steels - having less than 0.8% carbon. At high temperatures the
material is entirely austenite. Upon cooling it enters a region where the stable phases
are ferrite and austenite.
• Eutectoid steel - (carbon content 0.83%) entirely consists of pearlite.
• Hyper-eutectoid steels - are those that contain more than the eutectoid amount of
Carbon.
• Cast irons (carbon content from 2.06% to 4.3%) consist of proeutectoid cementite
CT ejected from austenite according to the curve ACM , peaiiite and transformed
ledeburite (ledeburite in which austenite transformed 10 pearlite).