Phase Diagrams

Mohammad Rais Alfiansyah Taufiq S.T., M.Sc.

Why Study this?
• Properties of materials determined by microstructure
• Change microstructure with thermal treatment
• Most phase diagrams are stable / equilibrium state / microstructure
• Some nonequilibrium structure more desirable due to better
properties

• Strong correlation between microstructure and mechanical

properties
Definition and Basics
• Components  pure metals or compounds form alloy
• Copper-Zinc brass  Cu and Zn
• Solute  a liquid that dissolves a solid, liquid or gaseous solute
• Solvent  a substance dissolved in another substance
• System  specific body of materials under consideration (ladle of
molten steel)
• Or series of possible alloys consisting of the same components
(iron-carbon system)
• Phase  a homogeneous portion of a system that has uniform
physical and chemical characteristics.
What is phase?
Solubility Limit
• Most alloys systems, specific
temperature  there is a
maximum concentration of solute
atoms in solvent
• Called as Solubility Limit
• Additional solute/compound
become another solid solution
having distinctly different
composition
Phase and Microstructure
• Pure metals are a phase
• Every solid, liquid and gaseous solution
• Example  Sugar-water syrup, solid sugar
• There is a boundary separating the phase
• Systems s composed of two or more phases are termed “mixtures” or
“heterogeneous systems.”
• Mixtures show distinguish properties compare to single phase

• Mechanical behaviour depend on microstructure

• Number of phases, their proportions, their distribution and arrangement
The Gibbs Phase Rule
• proposed by the nineteenth-century physicist J. Willard Gibbs

• P is the number of phases present

• F is termed the number of degrees of freedom (e.g., temperature,
pressure, composition)
• C represents the number of components in the system
• N s the number of noncompositional variables (e.g., temperature
and pressure).
Phase Equilibrium
• Definition
• Equilibrium  in terms of a thermodynamic quantity called the free energy
• Free energy  function of internal energy, randomness of atoms or molecules
• Equilibrium if free energy minimum in specific (temp, pressure, comp)
• Stable, no change indefinitely, change of (temp, pressure, comp)  higher free
energy
• In this context phase eq is condition where two phases or more exist in
a time
Metastable
• In solid systems, state of eq. never completely achieved due to
extremely slow rate of eq.
• Called as metastable or non-equilibrium
• Commonly more practical than equilibrium one
• Heat treatment in steel and aluminium
More in phase transformation
Phase Diagram
phase diagram / equilibrium diagram
the information about the control of the phase structure

Controllable parameters (temperature, pressure, and composition)

Phase diagrams constructed by these parameters

 One Component / Unary Phase
Diagrams
• Phase diagram of one-component
system, in which composition is
held constant
• unary phase diagram
• pressure–temperature (or P–T)
diagram
• Example of H2O
Binary Phase Diagrams
• Temperature and Composition as variable parameters, pressure
held constant ~~ 1 atm
• Consist of 2 components
• Maps that represent the relationships between temperature and the
compositions and quantities of phases at equilibrium  effecting
microstructure of alloys
Binary Isomorphous Systems
• Common example, Cu-Ni alloy
• Temperature  ordinate, composition  abscissa
• FCC crystal structure of Cu-Ni below 1080oC
• Cu-Ni soluble to each other, nearly identical atomic radii and
electronegativities, and similar valences

• isomorphous because of this complete liquid and solid solubility of

the two components.
• Liquid, solid solution, mixture (α+L)
• α,β,γ etc. represent solid solution of combined metals (alloys)
Determine phase weight fraction
• For α and L are straight forward, can be noted from abscissa
• But for α+L phase
Volume fraction
• For multiphase alloys, it is often more convenient to specify relative
phase amount in terms of volume fraction rather than mass fraction
Development of microstructure in
isomorphous alloys
• Equilibrium Cooling
1. Reducing temperature slowly considering equilibrium phase
2. Readjustment and redistribution
3. Diffusion
4. Long time
• Non-equilibrium Cooling
1. Fast cooling
2. Limit time for readjustment
3. Microstructure is different
 Equilibrium Cooling
• Start at a, 1300C L phase 35 wt% Ni-
65 wt% Cu
• At b, 1260C α start to grow, L (35 Ni)
and α (46 Ni)
• At c, L (32 Ni) and α (43 Ni)
• At d, almost all L alter to α, α (35 Ni)
and L (24 Ni)
• After d, 35 wt% Ni- 65 wt% Cu
• After all L alter to α, there is no new
phase
 Non-equilibrium Cooling
• Start at a’, 1300C L phase 35 wt% Ni-65
wt% Cu
• At b’, 1260C α start to grow, 46 wt% Ni-54
wt% Cu α(46Ni)]
• At c’, L (29 Ni) and α (40 Ni)
• Diffusion rate slowing as temperature
dropping, grain of α at c consist of 2 solid
layer α(46Ni) & α(40 Ni)
• Phase α with different Ni concentration
• Concentration represent with its average
 Non-equilibrium Cooling
• Rise of phase L fraction  drop of α fraction in α + L phase
• Solidus line shifting to higher Ni concentration
• At c’, solidus line show average Ni conc (α(42 Ni))
• At 1220C in non-eq cooling, solidification still on going
• Solidification will stop at e’, α(31 Ni) averaging α(35 Ni)

• The slower of cooling process, the smaller of displacement.

• Forming low-melting element at core (cored structure), can be prevented
with heat treatment  homogenization  atom diffusion
Mechanical properties of
isomorphous alloys
Binary eutectic systems
• Cu-Ag Alloy  binary eutectic system
• three single-phase regions are found on the diagram: a, b, and liquid
• The α phase  rich copper solution, silver solute, FCC structure
• The β phase  rich silver solution, copper solute, FCC
• Pure copper α, pure silver β
• the solubility in each of these solid phases is limited, Below BEG line
• Eutectic system :
• three phase may be
eq at eutectic
isotherm point
• Single phase
separated from each
other by two-phase
• Another example :
lead and tin  low
temperature solder

• CE (71.9 wt% Ag) and

TE 779C/1434F
quiz
• At 500°C (930°F), what is the maximum solubility
• (a) of Cu in Ag?
• (b) Of Ag in Cu?
Sn-Pb
 problem
• For a 40 wt% Sn–60 wt%
Pb alloy at 150?C (300?F),
(a) What phase(s) is (are)
present?
(b) What is (are) the
composition(s) of the
phase(s)?
(c) mass fraction and
(d) volume fraction. At 150C
take the densities of Pb and
Sn to be 11.23 and 7.24
g/cm3, respectively
• Composition of α
corresponds to tie line
α/(α+β) 10 wt% Sn–90 wt%
Pb
• Composition of β
corresponds to tie line
β/(α+β) 98 wt% Sn–2 wt%
Pb
• determine the density of each phase

• Volume fraction of β = 1 - volume fraction α

= 1 – 0,57 = 0,43
Development of microstructure in
eutectic alloys
 The iron–iron carbide (Fe–Fe3C)
phase diagram
Ferrite α BCC
Austenite γ FCC
 Ternary Phase Diagrams
These diagrams are based on those found in Phase Diagrams for Ceramacists (Levin et al., 1964).