PhaseDiagrams g

Phase ase Equilibria qu b a

A branch of chemical thermodynamics T understand To d t d the th stability t bilit and d composition iti of various phases in a chemical systems i involving l i one or more components. t Essential to those working with multiphase structures Includes all branches of engineering: Materials Engineering Metallurgy, Ceramics, Composites, Chemical Engineering

PhaseDiagrams g
PhaseDiagrams
Toolstoestimatethestabilityofvariousphasesofthe

chemical h i lsystemasaf function i of ftemperature, pressureandcomposition Graphicalrepresentationoftheequilibriumstateofa system Provideessentialinformationonanalyzing, controlling, g,improving p ganddeveloping p gpotential p materialssystems

PhaseDiagrams g
One of the most important sources of information

concerning i th behavior the b h i of f elements, l t compounds d and d solutions

Provide the knowledge of phase stability as a function of T, P

and dC
Permit us to study and control important processes such as Phase separation Solidification Sintering Purification Growth and doping of crystals

PhaseDiagrams
Principally, P Ds provide information about systems at

EQUILIBRIUM

But they can also assist in predicting nonEquilibrium phase

relations. Compositional changes and structures.

UsesofPhaseDiagrams
Useful to show the changes in phase compositions that can

occur during heat treatment processes that involve phase transitions, precipitation reactions, crystallization, etc.
Thermodynamic compatibility or lack of compatibility of

materials can be known

Indicate the degree of control needed for experimental

parameters during processing of materials. materials

In I systems involving i l i oxides, id the h effects ff of f changing h i

Temperature and/or oxygen partial pressure

Gases LiquidsandSolids Gases,

Any material can exist as gas, liquid or solid depending on

the relative magnitude of interatomic or intermolecular force over disruptive thermal forces
Generally, stability of different states of aggregation is a

function of P and T
For F example. l Increased I d pressure increase i the h interatomic i i

attraction of atoms of gas

System
The region under consideration, as distinguished from the

rest t of f the th universe i (th environment). (the i t)

Systems may be separated from environments by boundaries

that prevent the transfer of mass (a closed system), of heat ( adiabatic (an di b i system), ) or of f any energy (an ( isolated i l d system). )
Sometimes the word system is also used to refer to all

possible compositions defined by a particular set of components

Examples: ZrO2 system, PbSn system, MgOSiO2 system,

etc.

Phase
Any A portion i of f a system which hi h is i physically h i ll homogeneous h

within itself and bounded by a surface so that it is mechanically separable from any other portions
Practically ll speaking, k phases h are the h physical h l states of f matter

such as solids, liquids, and vapors.

Some phases have crystal structure (solids, including

minerals), others are amorphous (liquids, vapors, glasses).

Some only form with a definite chemical composition (pure

phases), others can take on a range of compositions (solutions).

Phase
Single Si l phase: h

Pure water liquid White gold AuAgNi: FCC metals mixed at atomic level Air a mixture of O2, N2, Ar, CO2, SO2, N2O etc. CaoZrO2 solid solution: Ca ion sitting on Zr site

Twophase:

Ice cubes in water Oil and water Milk: contains fat globules Glass ceramics: vision cookware: Pyroceram: glassy matrix and crystalline precipitates (change in atomic order)

Equilibrium
Equilibrium E ilib i i a condition is di i which hi h represents the h lowest l

energy state of the system

Properties are invariant with time Metastability: y steady y state achieved but could be more stable Ex: Diamond: formed under different conditions and brought g under ambient conditions Metallic glasses: if sufficient activation energy given by heating, crystalline state will be achieved

Component
A chemical formula that can be used to express the

compositional range available to a system.

It is important to think of components as mere mathematical

constructions, as basis vectors for expressing composition, and not to confuse them either with phases or species.
A measure of complexity p y A pure system, system in which all available phases have identical

composition, has one component. A system of two components is called binary

Note
It is critical to avoid confusing phases with components, components even

though they are often given the same name or symbol: e.g., quartz is a phase, phase whereas SiO2 is a component, component but the two might be interchanged in casual usage (as in "the quartz component" or "a component a silica phase phase").
The same component can often form many pure phases (H2O

can form steam, liquid water, and about ten different crystalline ice structures)
A given phase can often vary widely in composition within a

multidimensional component space (e.g., olivine, in which Mg Fe, Fe Ni, Ni Mn, Mn Co, Co the M crystal sites can be occupied by Mg, Ca, etc.).

Varaiance
The number of degrees of freedom or unconstrained

variables in a thermodynamic equilibrium assemblage, assemblage Th dimensionality di i li of f a region i i pressuretemperature The in composition space where a given phase assemblage can exist.

No. of phases N of No. f components

1 2 3

Pure water

Iceandwater(slush)

CaoZrO2

CCl4 andwater

Whitegold AuAgNi

Lithiumoxide AluminaSilica

GibbsPhaseRule
Establishes the number of thermodynamic variables that

must m t be experimentally e erimentall fixed fi ed in order rder to t fully f ll define the properties of an equilibrium chemical system
Mathematically

F= C P + 2
F= number of degrees of freedom or variance C= number of components P number P= b of f phases h present t at t equilibrium ilib i Constant 2= noncompositional thermodynamic variables (usually T and ) P)

GibbsPhaseRule
CaCO3 (s) = CaO (s)+ CO2 (g) Three different chemical constituents but number of

l TWO because b l l components are only any two can completely define the system in Eq.
F = CP+2

= 23+2 = 1

Only one variable either T or P can be changed independently

GibbsCondensedPhaseRule
For Onecomponent system, max. number of variables are

TWO (T and P) For Twocomponent (binary) system, max. THREE (T, P, C)

Solidliquid systems are usually studied @ constant pressure

and d so only l TWO variables i bl need d to be b considered id d Condensed phase rule: F=C P+1

Onecomponentsystem:purewater

Onecomponentsystem:purewater
At any yp point of f P, T water exists as solid, liquid q or vapor p

Curves represent points at which two phases coexist in Eq.

Triple point: All three phases coexist

Onecomponentsystem:purewater
hase t ansfo mations: Phase transformations:
Solid liquid : Liquid solid: Liquid Li id vapor: Vapor liquid: Solid vapor or vapor solid:

melting solidification evaporation ti condensation sublimation

Phase diagram delineates the boundaries of the phase fields But does not indicate q quantity y of f any yp phase

Onecomponentsystem:purewater
Negative slope of liquidsolid phase line
ice @ 2oC when subjected to high pressure,

ill transform f id H O will to li liquid H2O

Skating not on ice, but on water !!!!!!!!

A characteristic of materials having a higher coordination

number in liquid than in solid phase

For ex. H2O, Bi, Ge, Si

Liquid metals on the other hand will condense under pressure

t a solid to lid phase h

Onecomponentsystem:purewater
Specialty of water is that it contains more open bonding in

solid than in liquid

That means, , density y of f solid < density y of f liquid q water

Ice cubes FLOAT in water !!!!

@ 20 mm Hg pressure, water boils @ 20oC