Z.-G.

Ye CHEM 440/740

Chem 440/740 Solid State Mater. Chem.

Part II. Phase Equilibria, Phase Diagrams &

Phase Transformations
[Textbook, Chapter 7 (pp. 325 -357)+ Supplementary Mater.]

Importance of Phase Diagrams

Definitions/Terminology

The Gibbs Phase Rule

Interpretation of Phase Diagrams

One-Component Systems

Two-Component Systems

Three-Component Systems

[1] M. Hillert, “Phase Equilibria, Phase Diagrams & Phase Transformations” , Cambridge University Press, 2008. 1

Phase Diagrams 1
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1). Phase Diagrams & Their Importance

Phase Diagrams:
Graphical presentations of the stability of phases or
mixtures of phases under thermodynamic equilibrium
conditions, as a function of temperature (T), pressure (p) and
composition (x) in general, but also in terms of mechanical
stress (S), electric field (E), magnetic field (H), etc.

Phase Diagrams provide useful information on
(i) Composition of the phases present;
(ii) States of the phases (S, L, G, Plasma);
(iii) Structure & properties of the phases;
(iv) Transformations (Transitions) between the states,
e.g. melting/solidification, solid-solid transitions, etc;
(v) Chemical & thermal stabilities of the phases.
⇒ Applications to solid state synthesis, crystal growth, etc. 2

Phase Diagrams 2
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Examples of Phase Diagrams: One Component Systems

Pressure (P) – Temperature (T)

Three states/phases of H2O

Three phase boundaries:
AB: S/G; AD: L/S; AC: G/L.

Triple-point: A (S, L & G)

Supercritical point: C
Phase Diagrams
CHEM 440/740

Various solid phases of H2O

Polymorphic states:
Ice (I) – Ice (VI) (Polymorphs)

Multiple phase boundaries

Multiple triple-points: X, Z, A, B…
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Examples of Phase Diagrams: One-Component Systems

Phase Diagrams 4
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Examples of Phase Diagrams: Two-Component Systems

Tm(NaCl)
= 801 °C

Temperature (T) – Composition (x = NaCl [wt%])

Pressure = Constant (1 Atmosphere).

The melting point of ice is decreased.

The lowest melting point at : T = - 21.1 °C with x = 23.3% 5

Eutectic point; Eutectic behaviour.

Phase Diagrams 5
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Examples of Phase Diagrams: Two-Component Systems

Tm(MgO) Tm(SiO2)
= 2850 °C = 1650 °C

Temperature (T) – Composition (x = SiO2 [mol%])

Pressure = Constant (1 Atmosphere).

Formation of two compounds: Mg2SiO4 & MgSiO3

Different melting behaviours: Congruent & Incongruent 6

Complex phase behaviour.

Phase Diagrams 6
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Phase Diagram of
Ternary System
CaO – Al2O3 – SiO2

Phase Diagrams 7
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Ferroelectric LiNbO3 (LN) ・ LiTaO3 (LT) Single Crystals

Functions and Applications
Piezo--electrics
Piezo Pyro--electircs
Pyro
Volume change by
LN / LT single crystals
Electric current by
electric field temperature change

Pyro-sensor
SAW filter for mobile phone
IR sensor
TV・
・Video tuner

Conventional applications
Optical applications
Non--linear optics
Non
Electro--optics
Electro Frequency conversion
Refractive index change
by electric field Input Output

Input Output
Electric signal Gas monitor
→Light signal
Frequency converter
Optical modulator, Defect controlled single crystals ・ SHG blue, green
developed by NIMS ・OPO, OPG IR
switch
・ WDM mixer, filter
Holographic data
storage wide applications：
Infinitely ：Information technology, Laser processing, Laser therapy,
Display, Environment monitoring, Gas sensor, etc.

Phase Diagrams 8
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Importance of Phase Diagrams:

Nonstoichiometric Solid Solubility of LiNbO3
Li2O + Nb2O5 → 2LiNbO3
Congruent
stoichiometric composition
Temp. composition (Li : Nb = 48.5 : 51.5)
(℃) (Li:Nb = 50:50)

1200 liquid
LiNbO3
solid
solution
1100 Excess Nb+5 ion
LiNbO3 LiNbO3 at Li+1 ion site
+ +
Li3NbO4 LiNb3O 8
1000

Li2O 42 46 50 54 58 Nb2O5
Nb 2O5 (mol%)
Defect structure model
(Li0.95 ,Nb0.01 , 0.04 )NbO3 Number of defects in 1 cm cube
Nb Li 4 x 1019 V Li 16 x 1019

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Importance of Phase Diagrams:

Growth of Relaxor Ferroelectric Single Crystals of Complex Perovskite
Structure from the Pb(Mg1/3Nb2/3)O3 – PbO [PMN – PbO] System [1]

Morphology of an as-grown
PMN crystal.

Pseudo-binary Pb(Mg1/3Nb2/3)O3
[1] Z.-G. Ye, P. Tissot & H. Schmid, 10
– PbO phase diagram.
Mater. Res. Bull. 25, 739 - 748 (1990).

Phase Diagrams 10
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2). Definitions & Terminology

Phase: A homogeneous, physically distinct & mechanically
separable part of a system: Solid, Liquid, Gas, Polymorphs (S1,S2, ), …

The number of Phases: P (Gas, Liquid, Solid(s)…)

The Number of Components: C
• The minimum number of molecular species in terms of which
the composition of all the phases of a system may be quantitatively
expressed. See, e.g., the binary system of CaO-SiO2 (Fig. 7.1)

Chemical System:
• A substance or mixture of substances isolated from all
other substances, so that the chemical reactions & the effects
of pressure (p), temperature (T) and properties of
constituents can be investigated.

Variables: V or F
• Thenumber of independent variables (p, T, Composition x, E,
H) needed to define a system in equilibrium.
⇔ The (number) degrees of freedom of the system.
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Phase Diagrams 11
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Compositions, Components & Systems

Ternary system of Ca – Si – O (C = 3)

Pseudo-binary system of CaO – SiO2 (C = 2)
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Phase Diagrams 12
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3). The Phase Rule

The Phase Rule (J. W. Gibbs, 1876)
• The relationship between the
number of phases P, the number of
constituents C and the number of
variables V (or F) of a system:
P+V=C+2
• (Magic) Number 2 =
Temperature T + Pressure p

Applications: To all macroscopic
chemical systems, which are in a
state of equilibrium.

For solid state (condensed)
system with negligible vapor pressure,
p ≡ 1 atm., then “2” becomes “1”:
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P+V=C+1
+ The Phase Rule

Phase Diagrams 13
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4). Applications of The Phase Rule

4.1) One-Component Systems
• C = 1, V = 2 + 1 - P = 3 - P
• P = 1, V = 2 (T & p) ⇒ Area;
• P = 2, V = 1 (T or p) ⇒ Line;
• P = 3, V = 0 ⇒ Invariant at triple point
⇒ No variable can change (F = 0) !

Three states/phases of H2O:

P = 1, V = 2

Three phase boundaries:
AB: L/G; AD: L/S; AC: V/L.
P = 2, V = 1

Triple-point: A (S, L & G):
P = 3. V = 0 ⇒ Invariant point…
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Phase Diagrams 14
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4). Applications of The Phase Rule

4.1) One-Component Systems (cont’d)

Phase transitions (equilibria) between:
• Solid ↔ Liquid ↔ Vapour

• Phase transitions between polymorphic solid phases

(allotropes or polymorphs)
• Systems: General (Fig. 7.3), H2O (Fig. 7.4) and SiO2 (Fig. 7.5)

Fig. 7.3 Schematic phase

diagram of one component Fig. 7.5 Phase diagram of
system (C = 1) the SiO2 system
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Phase Diagrams 15
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4). Applications of The Phase Rule

4.2). Two-Component Systems
• C = 2, V = 4 - P
• For solid state system, p = 1 atm. : V = 3 – P
• P = 1, V = 2 (T and x) ⇒ Area;
• P = 2, V = 1 (T or x) ⇒ Line
• P = 3, V = 0 ⇒ Invariant!

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Phase Diagrams 16
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4). Applications of The Phase Rule

4.2). Two-Component Systems (cont’d)
4.2.1) Simple Eutectic Systems
• No intermediate compounds or solid solutions exist in solid state,
but only a mixture of solids (A + B) (Fig. 7.6)
4.2.2) Qualitative Interpretation Based on The Phase Rule
• Melting points of solids A & B at TmA & TmB, respectively;
• C = 1, P = 2, V = 0 → Invariant melting
• Congruent melting: Liquid and solid phases have the same
composition (i.e. no decomposition upon melting)
TmB

TmA

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Phase Diagrams 17
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4.2.2) Qualitative Interpretation Based on The Phase Rule

• Eutectic melting TE:
• Eutectic: A common melting (or crystallization) point for
both A & B solids
• Typically, TE < TmA or TmB
• Three phases: (SA + SB + LAB) coexist, P = 3
• V = 3 – P = 0 ⇒ Invariant melting/solidification point!
• At the eutectic composition xE:
⇒ Complete melting of the system
• At other binary compositions: Partial melting only

TmB

TmA

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Phase Diagrams 18
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• Liquidus:
• On the lines, solid & liquid phases are at equilibrium:
• P = 2, V = 1 ⇒ Only either T or x can vary!
• Liquid phase:
• A (single) liquid solution: P = 1, V = 2 ⇒ Both T & x can vary.
• Solidus line: The lowest temperature Tmin for the L phase
to appear (exist) (upon melting)
• Area of mixture of solid phases (T < TE):
P = 2 (SA + SB) ⇒ V = 1 (T)
• Areas of (Solid + Liquid): P = 2, V = 1 (T)
• (SA + L) or (SB + L): A or B is the primary phase
(1st phase to solidify), respectively.
• ⇒ Important for primary crystallization & crystal growth

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Phase Diagrams 19
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Cooling Curves, Crystallization Processes &

Eutectic Micro-texture of a Binary A – B System

Note: Measurements of cooling curves could be used to

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establish the relevant phase diagram(s), at least qualitatively.

Phase Diagrams 20
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4.2.3). Quantitative Phase Analysis (Fig. 7.6)

• T > Liquidus-T → Single liquid phase (L)
• Composition of L → To be read from the intersects of vertical line
with composition scale AB
• L → f , Read-off ⇒ (30%A + 70%B) ⇔ Overall composition
• T ↓ to T4:
• Liquid phase reaches liquidus point, g
• Solidification of first crystal of solid B → (Lg + δSB)
• Primary crystallization of SB

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Phase Diagrams 21
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4.2.3). Quantitative Phase Analysis (cont’d)

• T ↓ to T3: More SB has crystallized
• Lj becomes less rich in B
• L-composition moves from g to j’ ↔ j: (42%A + 58%B)
• Phase compositions: (Lj’ + SB↑)
• T ↓↓ to T2: More & more SB has crystallized
• L → Less & less rich in B → Composition h’ ↔ h: (57%A + 43%B)
• Phase compositions: (Lh’ + SB↑↑)

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Phase Diagrams 22
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• Relative amount of different phases, e.g. SB/Lh’ ?

• Tie-line: Line connecting the phases in equilibrium under
considerations
• Application of Lever Rule on the isothermal line h’-f ’-T2 (B’)
• Principle of moments with pivot point at f ’ & two weights at h’ & B’
• (amount of SB)x(distance f ’B’) = (amount of Lh’)x(distance h’f ’)
• Given that: (amount of SB) + (amount of Lh’) = 1
• (amount of SB)/(amount of Lh’) = h’f ’ / f ’B’ = h’f ‘/(h’B’ – f ’h’)
• (amount of SB) = h’f ‘/ B’h’ = hf / Bh = 27 / 57 = 47 % (at T2)
• (amount of Lh’) = f ‘B’/ h’B’ = f B / hB = 30 / 57 = 53% (at T2)

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Phase Diagrams 23
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• T2 ↑ to T3, h’f ‘ ↓ to j’f ’ → (amount of SB) ↓ to 29 % ⇒ Melting of SB ↑

• T2 ↓ to T1, h’f ‘ ↑ to yf ‘ → (amount of SB) ↑ to 57 % ⇒ Crystals of SB ↑

• At T = T1, SA starts to crystallize,

• P = 3 (Ly + SA + SB), V = 0 ⇒ Invariant
• At T ≥ T1, phase composition = (Ly + SB)
• At T ≤ T1, phase composition = (SB + SA)

“Forces & Moments”

(http://www.passmyexams.co.uk/GCSE/physics/turning-effect-forces.html)
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Phase Diagrams 24
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• Eutectic reaction at T1 (TE) = Const.: Ly → (SA + SB)

• As soon as SA appears, the phase composition of solids → (SA + SB)
• During the invariant reaction at T1: It moves on the solidus line
from B towards A (T1)
• Relative amount of two solids phases at an intermediate point S’
• (amount of SA) / (amount of SB) = BS’ / AS’
• With time ↑ (at T = T1), more & more SA appears → SA/SB ↑
• Relative amount of liquid Ly over two solids phases at S’
• (amount of Ly) / [amount of (SA + SB)] = (f ’’S’/ yf ’’)
• With time ↑ (at T1), f ‘’S’ ↓ → [Ly / (SA + SB)] ↓ ↔ Ly
solidification ↑

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Phase Diagrams 25
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• By the end of eutectic reaction T≤ T1:

• Composition of solids S’ reaches f ’’ → f ’’S’ = 0
• All Ly has solidified → (SA + SB)
• Final composition of solids (at f’’): (30%A + 70%B)
• ⇔ Composition of the initial liquid L !
• T < T1 ⇒ Further cooling of the mixture (30%SA + 70%SB) to f

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Phase Diagrams 26
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4.2.4). Liquidus, Saturation Solubility & Crystallization Pathway

• Liquidus ↔ Saturation solubility curve (limit) of A or B
• Above Curve yz → Homogeneous solution (Fig. 7.6)
• Below Curve yz → Crystallization of SB (Supersaturated solution in B)
• Liquidus ↔ Effect of soluble impurities (A) on the melting of pure B
• At T4 (< TmB), addition of a small amount of A to B → some liquid
phase appears ; A ↑ (30%) ⇒ A total liquid phase at point g
• Lowering of melting point of B from TmB to T4
• H2O-NaCl system:
• Eutectic melting at -21°C ⇒ Winter weather management!

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Phase Diagrams 27
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Chem 440/740 Solid State Mater. Chem.

Problem Set #1
(Phase Diagrams - I)
(1) Define the following terms: (a) A phase diagram, (b)
A chemical system, (c) A phase, (d) The number of
components, (e) The number of variables (or
degree of freedom).
(2) State the Gibbes Phase Rule and describe its
meanings.
(3) Apply the Phase Rule to one-component, two-
component and three-component systems.
(4) Discuss the crystallization pathway for various
binary systems, eutectic, peritectic and solid
solutions, and make quantitative analysis.
(5) Questions #7.1 – 7.7

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Phase Diagrams 28
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Chem 440/740 Solid State Mater. Chem.

Problem Set #1 (Phase Diagrams - I) (cont’d)

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Phase Diagrams 29