Phase Diagrams

Reading: Callister Ch. 10

What is a phase? What Wh t i is th the equilibrium ilib i state t t when h diff different t elements l t are mixed? What phase diagrams tell us. How phases evolve with temperature and composition (microstructures).
(lighter phase)

(darker phase)

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Phases
Phase: A homogeneous portion of a system that has uniform physical and chemical characteristics.
1 Diff 1. Different t physical h i l states: t t vapor, li liquid, id solid lid e.g. water

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Phases
2. Different chemical compositions

e.g. sugar water Solubility Limit: Max concentration for which only a solution occurs. Solubility limit increases with T: e.g., if T = 100C, solubility limit = 80wt% sugar.

Question: What is the solubility limit at 20C? Answer: 65wt% sugar. If Co < 65wt% sugar: syrup 3 If Co > 65wt% sugar: syrup + sugar.
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Components:
elements or compounds which are mixed initially
(e.g., Al and Cu)

Phases:
physically p ys ca y and a d chemically c e ca y d distinct s c regions eg o s that a result esu
(e.g., and ). AluminumCopper Alloy
(lighter phase) (darker phase)

Plain carbon steel

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Temperature and composition

B C

A: 2 phases present (liquid solution and solid sugar) B: Single phase C: back to 2 phases but at different composition Note: this is an equilibrium phase diagram (What does it mean to have phase equilibrium?)
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Phase Equilibrium
Equilibrium: minimum energy state for a given T, P, and composition (i (i.e. e equilibrium state will persist indefinitely for a fixed T, P and composition). An equilibrium phase will stay constant over time. Phase diagrams tell us about equilibrium phases as a function of T, P and composition (here, well always keep P constant for simplicity) simplicity).

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Unary Systems
Single component system Consider 2 elemental metals separately: Cu has melting T = 1085oC Ni has melting T = 1453oC
T

(at standard P = 1 atm)

T

liquid liquid 1453oC

1085oC solid

solid

Ni 7 What happens when Cu and Ni are mixed? 2007, 2008 Moonsub Shim, University of Illinois MSE280 Cu

Binary Isomorphous Systems

2 components Complete liquid and solid solubility Expect Tm of solution to lie in between Tm of two pure components T T liquid liquid L 1453oC

1085oC solid S

solid

0 Cu wt% Ni 2007, 2008 Moonsub Shim, University of Illinois

100 Ni

For a pure component, complete melting occurs before T increases (sharp phase transition). transition) But for multicomponent systems, there is usually a coexistence of L and S.
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Binary Isomorphous Systems

What can we learn from this phase diagram? 1. Phase(s) present.
A: solid () only B: solid and liquid

2. Composition of those phases

A: 60 wt% Ni B: 35 wt% Ni overall (how about in L and S separately?)

Solid-liquid coexistence region

3. Amount of the phases.

A: 100% phase B: % solid and % liquid?
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Determining phase composition in 2-phase region: 1. Draw the tie line. 2. Note where the tie line intersects the liquidus and solidus lines (i.e. where the tie line crosses the phase boundaries). 3. Read off the composition at the boundaries: Liquid is composed of CL amount of Ni (31 (31.5 5 wt% Ni) Ni). Solid is composed of C amount of Ni (42.5 wt% Ni).

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Lever Rule
Determining phase amount in the 2phase region: 1. Draw the tie line. 2 Determine 2. D t i th the di distance t f from th the point of interest (B) to each of the phase boundaries. R = Co CL S = C - Co 3. Mass fractions (wt%) of each phase: Liquid: WL =

C Co S 42.5 35 = = = 0.68 R + S C C L 42.5 31.5 C CL R 35 31.5 Solid: W = = o = = 0.32 R + S C C L 42.5 31.5

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i.e. 68% of the mass is liquid and 32% of the mass is solid.
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Lever Rule: Derivation

Since we have only 2 phases:

WL + W = 1

(1)

Conservation of mass requires that: Amount of Ni in -phase + amount of Ni in liquid phase = total amount of Ni or W C + WL C L = Co (2) From 1st condition, we have: Sub-in to (2):

W = 1 WL

(1 WL )C + WL C L = Co
WL = C Co C C L W = Co C L C C L

Solving for WL and W gives :

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Lever Rule: Derivation

A geometric interpretation: Co CL C R S

moment equilibrium:

WLR = WS 1 W
solving gives Lever Rule

WL

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Microstructures in Isomorphous Alloys

Microstructures will vary on the cooling rate (i.e. processing conditions) 1. Equilibrium Cooling: Very slow cooling to allow phase equilibrium to be maintained during the cooling process.

a (T>1260oC): start as
homogeneous liquid solution.

b (T ~ 1260oC): liquidus line reached. phase begins to nucleate. C = 46 wt% Ni; CL = 35 wt% Ni c (T= 1250oC): calculate composition
and mass fraction of each phase.

d (T~ 1220oC): solidus line reached. Nearly complete solidification.

C = 35 wt% Ni; CL = 24 wt% Ni

e (T<1220oC): homogeneous solid

solution with 35 wt% Ni.
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Example problem
65 wt% Ni 35 wt% Cu alloy is heated to T within ithi th the +L L region. i If -phase h contains 70 wt% Ni, determine:
a. Temperature of the alloy. b. Composition of the liquid phase. phases. c. Mass fraction of both p

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Non-equilibrium cooling
Fast cooling, but how fast? Fast w w.r.t. r t diffusion Since diffusion rate is especially low in solids, consider case where: Cooling rate >> diffusion rate in solid Cooling rate << diffusion rate in liquid (equilibrium maintained in liquids phase)

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a (T>1260oC): start as

Non-equilibrium cooling

homogeneous liquid solution. phase begins g to nucleate. reached. p

C = 46 wt% Ni; CL = 35 wt% Ni

b (T ~ 1260oC): liquidus line

c (T= 1250oC): solids that formed at pt b

remain with same composition (46wt%) and new solids with 42 wt% Ni form around the existing solids (Why around them?).

d (T~ 1220oC): solidus line reached. Nearly complete solidification.

Previously solidified regions maintain original composition and further solidification occurs at 35 wt% Ni.

e (T<1220oC): Non-equilibrium
solidification complete (with phase segregation). 2007, 2008 Moonsub Shim, University of Illinois
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Cored vs. Equilibrium phases

C changes as we solidify. Cu-Ni case: First to solidify has C = 46wt%Ni. Fast rate of cooling:
Cored structure
First to solidfy: 46wt%Ni Last to solidfy: < 35wt%Ni 35 t%Ni

L t to Last t solidify lidif h has C = 35wt%Ni. 35 t%Ni

Slow rate of cooling:

Equilibrium structure
Uniform C : 35wt%Ni

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Binary Eutectic Systems

Cu-Ag phase diagram
easily melted Single phase regions: -phase (solid solution rich in Cu). -phase (solid solution rich in Ag). L-phase (liquid solution). 2-Phase coexistence regions: + phases (limited solubility of Ag in Cu and vice versa lead to 2 different solid solution phases). +L and +L phase regions. Tie lines and Lever Rule can be applied in the 2-phase regions.

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Binary Eutectic System

Cu-Ag phase diagram
C =7wt% Ag CL = 50wt% Ag

Tie line

Tie line A

Calculate composition and mass fractions of each phases at points A and B B.

C = 3wt% Ag

C = 97wt% Ag

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Eutectic Point
Eutectic point: Where 2 liquidus lines meet (pt. E). Sometimes also referred to as invariant point. Eutectic Reaction: cool L(CE) (CE) + (CE) heat similar to one component (pure) system except p 2 solid p phases. Eutectic Isotherm: Horizontal solidus line at T = TE.

Cu-Ag phase diagram

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Eutectic System: Example

At 150oC for a 40wt% Sn/ 60 wt% Pb alloy: 1 What phases are present? 1. 2. What are the compositions of the phases present? 3. What are the mass fractions of the phases? 4. What are the volume fractions? For a 10wt% Sn/ 90wt% Pb alloy: 1. At what T, can a state with 50% liquid be achieved? 2. At 250oC, how much Sn must be added to achieve the same Pb-Sn phase diagram state (50% liquid)? 22 2007, 2008 Moonsub Shim, University of Illinois MSE280

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Microstructures in Eutectic Alloys

1. One component rich composition. a: start with homogeneous liquid. b: -phase solids with liquid. Compositions and mass fractions can be found via tie lines and lever rule. c: -phase solid solution only. Net result: polycrystalline solid. Cooling at this composition is similar to binary isomorphous systems.

Partial Pb-Sn phase diagram 2007, 2008 Moonsub Shim, University of Illinois

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Microstructures in Eutectic Alloys

2. One-component rich but cooling to + coexistence. d: homogeneous liquid. e: + L phase (same as previous but at different compositions and mass fractions). f: all -phase solid solution. g: + phase (passing through solvus line leads to exceeding solubility limit and phase precipitates out). Net result: polycrystalline -solid with fine crystals.

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Microstructures in Eutectic Alloys

3. Cooling through eutectic point. h: homogeneous liquid. i: solidification via eutectic reaction cool L(CE) (CE) + (CE) heat note: and phases have very different compositions than the original composition of the liquid (e.g. C = 18.3 wt% Sn; C = 97.8 wt% Sn whereas CL = 61.9 wt% Sn). Eutectic Structure: layered (lamellar) structure. Why does this structure form?
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Eutectic Structure
Pb-Sn Eutectic microstructure i t t

Sn

L
Pb

Pb rich Sn rich

In order to achieve large homogeneous regions, long diffusion lengths are required.

Lamellar structure forms because relatively short diffusion lengths are required.
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Microstructures in Eutectic Alloys

Hypoeutectic 4. Cooling through eutectic isotherm. j: homogeneous liquid. k: + L phases: use tie lines and lever rule. l: just above eutectic isotherm compositions given but what about mass fraction? m: remaining liquid transforms to eutectic structure upon crossing eutectic isotherm. Microconstituent: an element of a microstructure with identifiable and characteristic structure (at pt. m there are 2 microconstituents: primary 27 and eutectic structures) MSE280

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Just above the eutectic isotherm at C4:

WL =

P P+Q

All of this amount will turn into eutectic structure (We).

Primary structure:

Total (primary + eutectic):

Total (all in eutectic):

W ' =

Q P+Q

W =

Q+R P+Q+ R

W =

P P+Q+ R

Note: this is for equilibrium cooling. Non-equilibrium cooling will lead to: Cored primary phases & Increased fraction of eutectic microconstituent 28 2007, 2008 Moonsub Shim, University of Illinois MSE280

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T(C)
3 00

L L+ + L+

Adapted from Fig. 9.7, Callister 6e. (Fig. 9.7 adapted from Binary Phase Diagrams, 2nd ed., Vol. 3, T.B. Massalski (Editor-inChief), ASM International, Materials Park, OH, 1990.)

2 00 TE

(Pb-Sn System)

1 00

hypoeutectic
0 20 18.3 40

Co

hypereutectic
60 80 100 97.8

Co

C o , wt% Sn

eutectic
61.9

hypoeutectic: C
(Figs. 9.12 and 9.15 from Metals Handbook, 9th ed., Vol. 9, Metallography and Microstructures, American Society for Metals, Materials Park, OH, 1985.)

o =50wt%Sn

hypereutectic: (illustration only)

175 m

eutectic: C o =61.9wt%Sn

160 m micro-constituent
Adapted from Fig. 9.12, Callister 6e.

Adapted from eutectic Fig. 9.15, Callister 6e.

Adapted from Fig. 9.15, Callister 6e. (Illustration only)

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Congruent phase transformation

Congruent transformation: no change in composition upon phase transformation. Incongruent transformation: phase transformation where at least one of the phases go through composition change.

At what overall composition iti d does M Mg2Pb melt congruently?

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Intermetallic compounds
Intermediate (intermetallic) compounds: discrete metal compounds rather than solutions (i.e. distinct chemical formula). AxBy: in solution x and y can vary in compounds x and y are fixed (always fixed composition of A and B) B). Mg-Pb phase diagram

Can be considered as two phase diagrams put together back to back.

Mg-Mg2Pb phase diagram

Mg2Pb-Pb phase diagram

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Intermetallic compounds: Example

Within the + Mg g2Pb coexistence region, each of the two phases is found to have 50% mass fraction. If the overall composition is 50wt%Pb, determine the composition of each of the phases and temperature.

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Intermediate phases
Intermediate solid solutions (intermediate phases): Solid solutions that do not extend to pure components in the phase diagram. Cu-Zn Terminal solutions: and . Intermediate solutions: , , and . Tie lines and lever rule can be used to determine compositions and wt% of phases. e.g. at 800oC with 70 wt% Zn CL = 78 wt% Zn C = 67 wt% Zn
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Eutectoid and peritectic reactions

Eutectoid reaction: one solid phase turning into two other solid phases upon cooling
e.g. cool heat

Peritectic reaction: one solid phase transforms into liquid and a different solid phases upon heating cool
e.g. + L

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heat

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Ceramic phase diagrams

Al2O3-Cr2O3 MgO-Al2O3

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Gibbs Phase Rule

Number of phases present Number of non-compositional variables (Temperature & P Pressure) )

P+F=C+N
Degree of freedom (externally controllable parameters: i.e. T, P, and C) Number of components

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Gibbs Phase Rule

P+F=C+N
e.g. Cu-Ag phase diagram Cu and Ag are the only components -> C=2 Temperature is the only noncompositional variable here (i.e. fixed pressure). -> N = 1 (but in general N = 2) When 2 phases are present -> P = 2 which leads to F = C+N-P C+N P = 2+1-2 2+1 2 = 1 When only 1 phase is present -> P = 1 which leads to F = 2 What does this mean? Why should you care?
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Gibbs Phase Rule

In the previous example of Cu-Ag phase diagram, when F = 1, only one parameter (T or C) needs to be specified to completely define the system.

e.g. (for +L region) If T is specified to be 1000oC, compositions are already determined (C and CL). Or If composition of the a phase is specified to be C then both T and CL are already determined.
C CL
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Gibbs Phase Rule

When F = 2, both T and C have to be specified to completely define the state of the system. e.g.(for (f region) i ) If T is specified to be 800oC, C can be any where between 0 to ~8 wt% Ag) Or If composition of the a phase is specified to be C = 3 wt%, then T and can be any where between ~600 to 1100oC.
C
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Gibbs Phase Rule

Where in the CuAg diagram, is there a 0 degree of freedom? (i.e. T, P, and C are all fixed)

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Iron-Carbon System
Typical metal (e.g. Cu) T Liquid Tm Solid Iron T(oC) Liquid 1538 1394 -Fe (FCC) 912 -Fe (BCC) -Fe(BCC)

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Iron-Carbon System
Eutectic point

Eutectoid

Note: only goes out to 6.7 wt% C (100 wt% Fe3C intermediate compound)

FCC -phase has highest C concentration (2.14 wt% C) whereas BCC phase has low solubility (0.022 wt% C). Recall FCC is close packed (i.e. larger APF). Why is C more soluble in FCC? 42
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Eutectoid cooling
cool (0.76 wt% C) heat (0.022 wt% C) + Fe3C (6.7 wt% C)

Pearlite structure Layered structure forms due to the same reason as eutectic structure formation. 43 2007, 2008 Moonsub Shim, University of Illinois MSE280

Hypoeutectoid Alloys
Cooling below eutectoid composition. c: homogeneous solid. d: + coexistence. -phase nucleate at the grain boundaries (Why?). e -> f: - crossing eutectoid isotherm will cause all remaining -phase into eutectoid structure. - -phase that formed prior to eutectoid isotherm are called proeutectoid ferrite. Fraction of pearlite = W p =

Co 0.022 0.76 0.022

0.76 Co 0.76 0.022
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Fraction of proeutectoid = W ' = 2007, 2008 Moonsub Shim, University of Illinois

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Hypereutectoid Alloys
Cooling above the eutectoid composition Compositions and wt% can be f found d similarly i il l as h hypoeutectoid t t id cooling. Instead of proeutectoid , proeutectoid cementite appears.

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Example problem
For 0.35 wt% C, at T just below eutectoid isotherm determine: isotherm, a) Fractions of total ferrite and cementite phases. b) Fractions of proeutectoid ferrite and pearlite. c) Fraction of eutectoid ferrite.

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Influence of other alloying elements

Changes eutectoid T

Changes eutectoid composition

Useful processing info to control microstructure. 2007, 2008 Moonsub Shim, University of Illinois
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Concepts to remember
Phases, physical states, chemical composition, phase equilibrium. Phase diagrams tell us about:
Number N b and dt types of f phases h present. t Composition of each phase. Mass fraction (wt%) of each phase.

Binary isomorphous systems. Binary eutectic systems. Intermediate compounds. phases. Intermediate p Fe-C phase diagram. Microstructure evolution. Phase diagrams help us to determine the equilibrium microstructures which in turn determines the properties of materials!
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