Phase Equilibrium and Diagrams

Phenomenon
Ice melts into water at 0C and evaporates into gas at 100C Al becomes liquid at 660C Fe is BCC-structured (-Fe) below 912C, but FCCstructured (-Fe) between 912 and 1394C Al-Cu alloys can be strengthened by precipitation Fe can be hardened by quenching

Quantitative description
equilibrium phase diagrams what phases are present and how much of each phase at a certain temperature and alloying composition

Equilibrium microstructures
prediction from phase diagrams in typical systems

Terminology
phase: e.g. liquid, solid, gas, , , etc. (i.e. the structure) microstructure: what can be seen using a microscope
more descriptions will be given later

Reading: 9.1-9.9 (5th ed) 9.1-9.13 (6th ed)

Dr. K. Xia

436-220/222/280 Unit 2: Engineering Materials

Phase Equilibrium and Diagrams (2)

Concepts and Definitions Alloy: not pure metal Al-4 wt% Cu alloy Fe- 0.1 wt% C alloy (a carbon steel) Component: elementary constituent of an alloy Al and Cu Fe and C System: alloys of the same components with various compositions Al-Cu system (a series of alloys containing Al and Cu) Fe-C system

Phase: a homogeneous portion of a system that has uniform physical and/or chemical characteristics (i.e. you cannot tell any one part from any other part) chocolate bar with nuts (chocolate + nut) ice water: ice + water oil in water: oil + water two much sugar in coffee (solid sugar + sweet liquid coffee) Pearlite steel: -Fe + Fe3C precipitation strengthened AlCu alloy: Al + fine particles of CuAl2
A system may contain only one phase or multiple phases depending on the composition, temperature, pressure and other conditions

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (3)

Phase equilibrium e.g. water at 25C a system is at equilibrium if the when a system is at number of phases and their Concept of equilibrium, it attains a amounts do not change with free energy minimum energy state (with will be taught time minimum free energy) and is in thermosaid to be stable dynamics e.g. ice in water at 0C when a system at equilibrium if no heat exchange contains multiple phases, the with the environment phases are at equilibrium with dynamic: any ice each other or phase melting will absorb heat equilibrium is reached and cause freezing of Phase equilibrium may be water at the same time, destroyed if conditions are i.e. although the total changed, most notibly by amount of ice does not temperature changes change, the melting and freezing processes liquid water changes into vapor proceed at the same if T is raised to " 100C rate to keep the Fe changes from BCC to FCC equilibrium when T is raised to " 912C
436-220/222/280 Unit 2: Engineering Materials Dr. K. Xia

Phase Equilibrium and Diagrams (4)

Microstructure Metastable state in addition to the number of an observed state of a system phases and the amount of each does not necessarily indicate phase, microstructure tells the that the system has attained shape and size of each phase the lowest energy possible, and their distribution in space e.g. diamond (C) has higher free energy than graphite (C) at ambient conditions, but do not loose your sleep as your precious diamond is not going to become cheap pencil lead A: host A: host A: host overnight (the energy barrier is B: dissolved B: fine B: lamellae in A particles too high for the change to take place at any detectable rate)! microstructure is important as it often determines the properties of materials (e.g. nominally same materials with same compositions and phases may have very different strengths)
Dr. K. Xia

We will discuss the topic of phase transformation in more details later

436-220/222/280 Unit 2: Engineering Materials

Phase Equilibrium and Diagrams (5)

Equilibrium Phase Diagrams

What phases are there under a certain conditions ( e.g. T) for a given alloy (i.e. composition) and what changes will occur if T is pure Cu altered (phase transformation)? Other For pure metals (i.e. one conditions component system) such as pressure are Al (melting T = 660C) usually solid (FCC): <660C constant liquid: > 660C Fe (melting T = 1538C) solid (BCC): < 912C solid (FCC): 912-1394C solid (BCC): 1394-1538C Tm of liquid: > 1538C pure Cu
A diagram is necessary if a system consisting of 2 or more components 436-220/222/280 Unit 2: Engineering Materials

Binary isomorphous systems involving two components at ambient atmosphere (P = 1 atm) two axes are needed: T and C
pure Ni Tm of pure Ni

liquid field + L two phase field lower limit of the liquid field upper limit of the solid field

alpha field : solid solution of Cu and Ni (FCC)

Dr. K. Xia

Phase Equilibrium and Diagrams (6)

Phase present A: Cu-60Ni at 1100C B: Cu-35Ni at 1250C

The T and composition define the point in the diagram

Compositions of phases present A: = 40 wt% Cu-60 wt%Ni (same as the alloy composition) B: CL L = 68.5 wt% Cu-31.5 wt%Ni C = 57.5 wt% Cu-42.5 wt%Ni
CL and C are different from the alloy composition Co

a mixture of and L

100% phase

IMSE: Phase Diagrams

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (7)

Amounts of phasees present A: 100% (single phase) B: using the lever law
WL = W =

S C Co 42 .5 35 = = = 68 % R + S C C L 42 .5 31 .5 R C CL 35 31 .5 = o = = 32 % R + S C C L 42 .5 31 .5

mass fraction of liquid mass fraction of

W + W L = 100 %

If there are 100 g of alloy B, the amount of liquid phase at 1250C is 68 g and that of is 32 g. Total amount of Cu in liquid = CL 68.5% x 68 g = 46.6 g Total amount of Cu in = C 57.5% x 32 g = 18.4 g
Cu Cu

x 68 g =

x 32 g =

Total amount of Cu in alloy B is 46.6 + 18.4 = 65 g This is the same if we calculate the total amount of Cu using 100 g x 65% = 65 g
Referring to example 9.1

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (8)

Microstructures following equilibrium cooling of Cu-35Ni from ~1300C To to T1: cooling of starting temperature liquid (35Ni) T1 just under T1: T2 (~46Ni) nucleation starts (L: ~35Ni) T3 at T2: L: 32Ni T4 : 43Ni WL: 27.3% using lever law W : 72.7% at T3: solidification finishes (100% : 35Ni) T3 to T4: cooling of
436-220/222/280 Unit 2: Engineering Materials

very slow cooling, i.e. the system is given as much time as needed to reach equilibrium at each temperature

To

Diffusion is necessary which is a slow process

How can such a change of composition be realised in ?

alloy

Dr. K. Xia

 Microstructures following nonequilibrium cooling To To to T1: cooling of liquid The core (35Ni) with just under T1: (~46Ni) 46Ni T1 nucleation starts (L: The solidifying ~35Ni) average: 46Ni T2 layer with at T2: L (29Ni) and : 40Ni T3 40Ni average: 42Ni The T4 solidifying at T3: L (24Ni) and : layer with 35Ni average: 38Ni 35Ni T5 at T4: L (21Ni) and : The solidifying 31Ni average: 35Ni layer with 31Ni T4 to T5: cooling of solidification with an average 35Ni finishes at T4, Segregation (consisting of layers of not T3 ! /coring different compositions)
Can the extent of segregation be reduced? 436-220/222/280 Unit 2: Engineering Materials

cooling is fast to allow little diffusion in (diffusion in liquid is taken to be still fast enough to allow equilibrium to be reached)

Phase Equilibrium and Diagrams (9)

average composition of

alloy

Dr. K. Xia

Phase Equilibrium and Diagrams (10)

Binary eutectic systems

Eutectic isotherm
: solid solution based on Cu with dissolved Ag : solid solution based on Ag with dissolved Cu

solubility limit (how much solute can be dissolved in the host). e.g. at 600C, Cu can dissolve a maximum of ~3.1 wt% Ag

Eutectic or invariant point

~3.1 436-220/222/280 Unit 2: Engineering Materials Dr. K. Xia

Phase Equilibrium and Diagrams (11)

Eutectic or invariant point

Eutectic isotherm

L (CE) = (C E) + (C E) Eutectic reaction

The eutectic reaction takes place at a constant temperature (TE = 779C). At the end of the reaction, all liquid has become and and their relative amounts can be calculated by using the lever law (W = 19.3/83.2 = 23.2% and W = 76.8%).

Alloy: Cu-71.9Ag

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (12) Examples 9.2 and 9.3

Homework: do the same for alloy A (20Sn) at 250C, alloy D (90Sn) at 200C, and alloy X (50Sn) at TE just before the eutectic reaction and just after the completion of the eutectic reaction, respectively.

Pb-40Sn alloy at 150C + two phases C: Pb-10Sn C: Pb-98Sn W = 58/88 = 66% W: = 30/88 = 34%
Hint: just before the eutectic reaction there are two phases, L + ; just after the reaction there are two phases, + .

A D X
61.9 97.8

TE = 183C 18.3

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (13)

Microstructures following equilibrium cooling alloy C1 T > T1: 100% L at T1: solidification of starts at T2 solidification of finishes < T2: 100%

T1 T2

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (14)

alloy C2 T > T1: 100% L at T1: solidification of starts at T2 solidification of finishes at T3: precipitation of starts (in the matrix) < T3: W as T (using the lever law) < T4: no more change

Composition of L T1

T2 T3

Composition of T4

Compositions of are out of range

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (15)

alloy C3 T > TE: 100% L just reach TE: cosolidification of + starts at TE: eutectic reaction continues until all L has become the alternating eutectic and structure lamellae < TE: C and C change along the respective solvus lines
436-220/222/280 Unit 2: Engineering Materials

The relative amount of each phase at a particular temperature can be calculated by using the lever law

TE

Dr. K. Xia

Phase Equilibrium and Diagrams (16)

alloy C4

HW: do the same analysis for alloy Pb-90Sn

Just before TE: +L W = 21.9/43.6 = 50.2% WL = 21.7/43.6 = 49.8% at TE: L (61.9) = (18.3)+ (97.8) eutectic structure Just after TE: + W = 57.8/79.5 = 72.7% W = 21.7/79.5 = 27.3% HW: what happens during cooling from TE to room temperature?

At T1, solidification starts

T1

TE

18.3

61.9

97.8

This microstructure consists of primary and a eutectic + (lamellar) structure

HW: how much of the eutectic structure in the final material?

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (17)

Binary systems with intermediate intermetallic compounds

Intermetallic compound

436-220/222/280 Unit 2: Engineering Materials

Dr. K. Xia

Phase Equilibrium and Diagrams (18)

Binary systems with intermediate phases and reactions

Read 9.8 & 9.9 (5th ed), 9.12 & 9.13 (6th ed)

Intermediate solid solution Peritectic reaction +L=

Terminal solid solution

Eutectoid reaction

436-220/222/280 Unit 2: Engineering Materials

=+

Dr. K. Xia

Phase Equilibrium and Diagrams (19) - Summary

Terminology system component phase microstructure equilibrium Equilibrium phase diagram (binary) fields: single phase, two phase tie lines phases present composition of each phase amount of each phase - the lever law eutectic reaction segregation due to nonequilibrium cooling
436-220/222/280 Unit 2: Engineering Materials

Microstructure upon cooling from liquid to room temperature process change of composition during cooling change of amount of each phase during cooling change of microstructure during cooling and the final microstructure

Dr. K. Xia

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