# Chapter 9: Phase Diagrams

• When we combine two elements...
what equilibrium state do we get?

• In particular, if we specify...
--a composition (e.g., wt% Cu - wt% Ni), and --a temperature (T )

then...
How many phases do we get? What is the composition of each phase? How much of each phase do we get?

Phase A
Nickel atom Copper atom

Phase B

Chapter 9 - 1

Phase Equilibria: Solubility Limit
Introduction – Solutions – solid solutions, single phase – Mixtures – more than one phase Adapted from Fig. 9.1,
Callister 7e.

• Solubility Limit:
Temperature (°C)

Sucrose/Water Phase Diagram
100 80 60 40 20 Solubility Limit

Max concentration for which only a single phase solution occurs.

L
(liquid)

Question: What is the
solubility limit at 20°C?

L
(liquid solution i.e., syrup)

+ S
(solid sugar)

Pure Water

Chapter 9 - 2

Pure Sugar

If Co < 65 wt% sugar: syrup 0 20 40 6065 80 100 If Co > 65 wt% sugar: syrup + sugar. Co =Composition (wt% sugar)

1

. syrup) + S (solid sugar) A (20°C.. 9.90) 100 Temperature (°C) 1 phase 2 phases 80 60 40 20 0 0 L (liquid) watersugar system L (liquid solution i.4 2 . Al and Cu) • Phases: The physically and chemically distinct material regions that result (e. Chapter 9. B (100°C. AluminumCopper Alloy β (lighter phase) α (darker phase) Adapted from chapter-opening photograph.e.70) 2 phases Adapted from Fig.g. • Changing Co can change # of phases: path B to D.Components and Phases • Components: The elements or compounds which are present in the mixture (e. α and β).. Callister 7e.70) D (100°C. 20 40 60 70 80 100 Co =Composition (wt% sugar) Chapter 9 .g.3 Effect of T & Composition (Co) • Changing T can change # of phases: path A to B. Chapter 9 .1. Callister 3e.

g.8 • Both have the same crystal structure (FCC) and have similar electronegativities and atomic radii (W. • For this course: -binary systems: just 2 components. 9.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys. P. Hume – Rothery rules) suggesting high mutual solubility.5 Phase Diagrams • Indicate phases as function of T. Ni-Cu solution) Crystal Structure Ni Cu FCC FCC electroneg r (nm) 0. -independent variables: T and Co (P = 1 atm is almost always used). L α (FCC solid solution) 40 60 80 u lid so 100 wt% Ni Chapter 9 . Co. 9. Materials Park. ASM International.1246 0. and P.6 3 . OH (1991).Phase Equilibria Simple solution system (e. Callister 7e. Chapter 9 . (Fig. Nash (Ed.1278 1.3(a). • Ni and Cu are totally miscible in all proportions.9 1.). T(°C) • Phase Diagram for Cu-Ni system 1600 1500 1400 1300 1200 1100 1000 0 20 liq us uid • 2 phases: L (liquid) + αs L (liquid) α (FCC solid solution) • 3 phase fields: L L+α α Adapted from Fig..

1100 1000 0 20 40 A(1100°C. 35): 2 phases: L + α T(°C) 1600 L (liquid) B (1250°C. Materials Park. then we know: --the # and types of phases present. isomorphicity means having the same crystal structure or complete solid solubility for all compositions.60) 60 80 100 wt% Ni Chapter 9 . Nash (Ed.3(a). (Fig.• Note:The Ni-Cu alloy system shown in the previous slide is a binary isomorphous system.35) 1500 1400 1300 1200 u liq s idu us lid so α α L +(FCC solid solution) Cu-Ni phase diagram Adapted from Fig.3(a) is adapted from Phase Diagrams of Binary Nickel Alloys. P. ASM International. In the phase diagram sense. 9. • Examples: A(1100°C. • Note: Isomorphous : Having the same structure. Callister 7e.8 4 . 1991). OH. 9. Chapter 9 .). 60): 1 phase: α B(1250°C.7 Phase Diagrams: # and types of phases • Rule 1: If we know T and Co.

Cu-Ni system A L (liquid) tie line dus i l i qu • Examples: Co = 35 wt% Ni At T A : Only Liquid (L) W L = 100 wt%. Cα = C solidus ( = 43 wt% Ni here) International.10 5 .).Phase Diagrams: composition of phases • Rule 2: If we know T and Co. OH.9 Phase Diagrams: weight fractions of phases • Rule 3: If we know T and Co. Materials Park. Materials Park.) Chapter 9 .3(b) is adapted from Phase Diagrams of Binary Nickel Alloys. 9. T(°C) Cu-Ni system • Examples: A TA Co = 35 wt% Ni tie line dus i l i qu 1300 L (liquid) At T A = 1320°C: α L+ s Only Liquid (L) B idu TB s ol CL = Co ( = 35 wt% Ni) α α At T D = 1190°C: L+ (solid) 1200 D Only Solid ( α) TD Cα = Co ( = 35 wt% Ni) 20 30 35 4043 50 32 At T B = 1250°C: CLCo Cα wt% Ni Both α and L Adapted from Fig. then we know: --the amount of each phase (given in wt%). W α = 0 At T D: Only Solid ( α) W L = 0. Phase Diagrams CL = C liquidus ( = 32 wt% Ni here) (Fig. 1991. ASM International. 9.) Chapter 9 . OH. Wα = 100 wt% At T B : Both α and L T(°C) TA 1300 TB 1200 L +α B R S D CLCo L+ s α α (solid) 50 us olid TD 20 WL = Wα = 43 − 35 S = = 73 wt % R + S 43 − 32 30 35 32 40 43 Cα wt% Ni R = 27 wt% R +S Adapted from Fig.3(b). 1991.). Callister 7e. P. 9. then we know: --the composition of each phase. ASM of Binary Nickel Alloys. 9.3(b) is adapted fromNash (Ed. Nash (Ed. P. Callister 7e. (Fig.3(b).

e. 2 components: Cu and Ni.4.. A 35 B C D 36 L+ 46 43 α Cu-Ni system --isomorphous i. 9. Callister 7e.e. 9. L: 32 wt% Ni α: 43 wt% Ni L: 24 wt% Ni α: 36 wt% Ni L +α E α (solid) 1100 20 30 • Consider Co = 35 wt%Ni.The Lever Rule • Tie line – connects the phases in equilibrium with each other .essentially an isotherm T(°C) 1300 L (liquid) B L+ α R tie line dus i l i qu How much of each phase? Think of it as a lever (teeter-totter) ML Mα L+ α TB 1200 α (solid) S 50 idu s ol s R S 20 30C C 40 C α L o M α ⋅S = M L ⋅R R C − CL = 0 R + S Cα − CL Chapter 9 .11 wt% Ni Adapted from Fig..12 6 . α phase field extends from 0 to 100 wt% Ni. 35 Co 40 50 wt% Ni Chapter 9 . WL = ML S C − C0 = = α M L + M α R + S C α − CL Wα = Ex: Cooling in a Cu-Ni Binary • Phase diagram: Cu-Ni system. T(°C) L (liquid) 130 0 L: 35 wt% Ni α: 46 wt% Ni 32 24 1200 L: 35wt%Ni • System is: --binary i.3(b). Adapted from Fig. complete solubility of one component in another. Callister 7e.

--Peak as a function of Co --Min.6(b).Cored vs Equilibrium Phases • Cα changes as we solidify. • Fast rate of cooling: Cored structure First α to solidify: 46 wt% Ni Last α to solidify: < 35 wt% Ni Last α to solidify has Cα = 35 wt% Ni. as a function of Co Chapter 9 . 9.%AR) Elongation (%EL) 60 50 40 30 20 0 20 Cu 40 60 80 100 Ni %EL for pure Cu %EL for pure Ni 400 TS for pure Ni TS for pure Cu 200 0 20 40 60 80 100 Cu Ni Adapted from Fig.14 7 . wt% Ni Composition. Callister 7e. wt% Ni Adapted from Fig.13 Mechanical Properties: Cu-Ni System • Effect of solid solution strengthening on: --Tensile strength (TS) Tensile Strength (MPa) --Ductility (%EL. • Cu-Ni case: First α to solidify has Cα = 46 wt% Ni. 9. • Slow rate of cooling: Equilibrium structure Uniform C α: 35 wt% Ni Chapter 9 . 300 Composition.6(a). Callister 7e.

Callister 7e.0 71.7. 9. melting TE composition 200 • Eutectic transition 0 20 40 60 CE 80 100 L(CE) α(CαE) + β(CβE) Co . β) α L + α 779°C • Limited solubility: L+β β 800 TE α: mostly Cu 8.CO S = β Wα = R+S Cβ . find..11 29 = = 33 wt% = 99 . melting T.16 8 .Cα R+S 40 .Binary-Eutectic Systems 2 components has a special composition with a min.11 88 0 11 20 Cα 40 Co 60 80 C.8.3 183°C --the relative amount of each phase: C .9 97. --the phases present: α + β T(°C) --compositions of phases: CO = 40 wt% Sn Cα = 11 wt% Sn Cβ = 99 wt% Sn 300 Pb-Sn system L (liquid) α L+ α 18.: Cu-Ag system T(°C) 1200 Cu-Ag system • 3 single phase regions L (liquid) 1000 (L. α.40 59 = = 67 wt% 99 .8 R S α+β 99 . Chapter 9 .9 91. Chapter 9 .11 88 C . Callister 7e. 9.2 β: mostly Ag 600 • TE : No liquid below TE α+β 400 • CE : Min. wt% Ag Adapted from Fig. wt% Sn 99100 Cβ Adapted from Fig.. Ex.15 EX: Pb-Sn Eutectic System (1) • For a 40 wt% Sn-60 wt% Pb alloy at 150°C.Cα = 200 150 100 L+β β 61.Cα Wβ = R = O Cβ .

Cα C.18 9 . Microstructures in Eutectic Systems: I • Co < 2 wt% Sn • Result: --at extreme ends --polycrystal of α grains i.Cα = WL = = 79 wt% 29 CL .. 0 Co 10 20 30 o 2 (room T solubility limit) C . wt% Sn Chapter 9 .17 Adapted from Fig. only one solid phase.EX: Pb-Sn Eutectic System (2) • For a 40 wt% Sn-60 wt% Pb alloy at 200°C. Callister 7e.. wt% Sn Chapter 9 .CO 46 . --the phases present: α + L T(°C) --compositions of phases: CO = 40 wt% Sn Cα = 17 wt% Sn CL = 46 wt% Sn 300 220 200 Pb-Sn system --the relative amount of each phase: Wα = CL . T(°C) 400 L α 300 L: Co wt% Sn L α α: Co wt% Sn L+ α (Pb-Sn System) 200 TE 100 α+ β Adapted from Fig. 9.40 = CL . Callister 7e. find. 9.8.17 6 = = 21 wt% 29 α L+α R L (liquid) S 183°C L+β β 100 α+β 0 17 20 Cα 40 46 60 Co CL 80 100 23 CO .11.e.Cα 46 ..

Callister 7e. Callister 7e.3 wt% Sn 400 • Result: L L: Co wt% Sn Initially liquid + α then α alone finally two phases α polycrystal fine β-phase inclusions 300 L+α 200 L α α: Co wt% Sn α TE α β 100 α+ β Pb-Sn system Sn Adapted from Fig. 9. Callister 7e.8 wt% Sn α: 18.3 40 β: 97. wt% Sn 100 97.9 80 C.3 wt%Sn Adapted from Fig.19 Microstructures in Eutectic Systems: III • Co = CE • Result: Eutectic microstructure (lamellar structure) --alternating layers (lamellae) of α and β crystals.12. T(°C) L: Co wt% Sn Micrograph of Pb-Sn eutectic microstructure 300 Pb-Sn system 200 TE L α L+α 183°C L+β β 160 μm Adapted from Fig. 9. (sol. 60 CE 61.3 (sol.20 10 .14. 100 α+β 0 20 18. wt% 2 limit at T room ) 18. 10 20 30 Co Co .Microstructures in Eutectic Systems: II T(°C) • 2 wt% Sn < Co < 18.8 Chapter 9 .13. limit at TE) 0 Chapter 9 . 9.

Cα = 18.16.3 wt% Sn Cβ = 97.Wα) = 50 wt% Pb-Sn system 200 TE L α L+α R S L α L+β β S R • Just below TE : primary α eutectic α eutectic β 100 α+β 0 20 18. Callister 7e.15.Lamellar Eutectic Structure Adapted from Figs. 9.8 wt% Sn Wα= S = 73 wt% R+S Wβ = 27 wt% Chapter 9 .8 Adapted from Fig. 9.3 40 60 61.3 wt% Sn CL = 61.9 80 100 97.22 Co.3 wt% Sn < Co < 61. wt% Sn 11 .9 wt% Sn S Wα = = 50 wt% R+S WL = (1.14 & 9.21 Microstructures in Eutectic Systems: IV • 18.9 wt% Sn • Result: α crystals and a eutectic microstructure T(°C) 300 L: Co wt% Sn α L • Just above TE : Cα = 18. Chapter 9 . Callister 7e.

9. Chapter 9 . (Illustration only) Chapter 9 . Callister 7e.B. Adapted from Fig. 9.17.9 80 100 Co.8 200 adapted from Binary Phase TE Diagrams. 9.9 wt% Sn β β 160 μm eutectic micro-constituent Adapted from Fig.17 from Metals Handbook.) 0 (Figs. T. 9. 9th ed. Mg2Pb Note: intermetallic compound forms a line . (Fig. Massalski (Editor-inChief). Metallography and Microstructures.e. composition) is exact.23 Intermetallic Compounds Adapted from Fig.. Vol. 1985. 2nd ed.8. Callister 7e. β β β β Adapted from Fig. wt% Sn hypoeutectic: Co = 50 wt% Sn hypereutectic: (illustration only) α α α α α α 175 μm eutectic: Co = 61. ASM International. 9.14 and 9. 9.14.not an area because stoichiometry (i. 100 Materials Park. Callister 7e. Callister 7e. OH.17. American Society for Metals.) L α L+α α+β L+β β (Pb-Sn System) 20 40 60 eutectic 61.20. 3.. 9. Materials Park. OH. 1990.24 12 . 9.Hypoeutectic & Hypereutectic 300 T(°C) Adapted from Fig. Callister 7e. Vol.

liquid + solid 1 S1 + L S2 cool δ + L heat γ solid 2 (Fig 9.25 Eutectoid & Peritectic Cu-Zn Phase diagram Peritectic transition γ + L δ Eutectoid transition δ γ+ε Adapted from Fig.21) (1493ºC) Chapter 9 . Chapter 9 . 9.cementite cool γ α + Fe3C (727ºC) heat • Peritectic(包晶) .liquid in equilibrium with two solids L cool α + β heat • Eutectoid(共析) .26 13 . Callister 7e.Eutectoid & Peritectic • Eutectic(共晶) .21.solid phase in equation with two solid phases intermetallic compound S2 S1+S3 .

(Fig.Callister 7e. OH.) C eutectoid 120 μm 400 0 (Fe) Hypoeutectoid Steel T(°C) 1600 γ α+ B S 727°C = T eutectoid R α+Fe3C 4 5 6 0. 9.27. wt% C Fe3C (cementite-hard) α (ferrite-soft) Chapter 9 .24.Callister 7e. 2nd ed.28 14 . T. 9.30.29. Massalski (Ed. Materials Park. 1990.24 adapted from Binary Alloy Phase Diagrams. 9.30 Co.. Callister 7e. ASM International. 9.Iron-Carbon (Fe-C) Phase Diagram • 2 important points -Eutectic (A): L ⇒ γ + Fe3C T(°C) 1600 δ 1400 1200 1000 800 600 L Fe3C (cementite) γ +L γ (austenite) γ γ γ γ 1148°C A γ +Fe3C -Eutectoid (B): γ ⇒ α +Fe3C L+Fe3C R S α Result: Pearlite = alternating layers of α and Fe3C phases (Adapted from Fig.) γ + Fe3C r s 727°C w α =s/(r +s) 600 w γ =(1. δ 1400 L Fe3C (cementite) γ +L γ (austenite) 1148°C γ γ γ γ γ γ γ γ αγ 1200 1000 800 L+Fe3C (Fe-C System) Adapted from Figs.Callister 7e.76 400 0 (Fe) pearlite 6. wt% C 100 μm Hypoeutectoid steel w pearlite = w γ w α =S/(R+S) w Fe3C =(1-w α ) pearlite Adapted from Fig.7 Co . 9. 1.B.24 and 9.76 1 2 4.-inChief).7 Adapted from Fig.27 3 6. Vol.wα ) α γ γ γ α α αRS 1 C0 α + Fe3C 2 3 4 5 6 0. proeutectoid ferrite Chapter 9 .

) 6. determine the following a) composition of Fe3C and ferrite (α) b) the amount of carbide (cementite) in grams that forms per 100 g of steel c) the amount of pearlite and proeutectoid ferrite (α) Chapter 9 .B. Materials Park.76 α +Fe3C 4 5 6 400 0 (Fe) pearlite Adapted from Figs. 2nd ed.Hypereutectoid Steel T(°C) 1600 δ 1400 L γ +L γ (austenite) 1148°C γ γ 1000 800 γ +Fe3C r s S 1 Co 2 3 Fe3C (cementite) γ γ γ γ Fe3C γ γ (Fe-C System) L+Fe3C 1200 w Fe3C =r/(r +s) 600 w γ =(1-w Fe3C ) γ γ γ γ α R 0.Callister 7e.29 Example: Phase Equilibria For a 99. (Fig. proeutectoid Fe3C Chapter 9 . 9. wt%C 60 μmHypereutectoid steel w α =S/(R+S) w Fe3C =(1-w α ) pearlite Adapted from Fig. ASM International. T.. 1. Massalski (Ed. 9.-inChief). 1990.7 w pearlite = w γ Co .24 and 9.6 wt% Fe-0. 9.33. Vol.24 adapted from Binary Alloy Phase Diagrams.30 15 .40 wt% C at a temperature just below the eutectoid. OH.Callister 7e.32.

Chapter 9 – Phase Equilibria Solution: a) composition of Fe3C and ferrite (α) b) the amount of carbide (cementite) in grams that forms per 100 g of steel δ Co − Cα Fe3C 1400 = x100 T(°C) Fe3C + α CFe3C − Cα 1600 CO = 0.31 CFe 6.40 wt% C Cα = 0.4 − 0.022 Fe3C = 5.70 wt% C 3 L L+Fe3C 0.40 wt% C Cα = 0.32 Fe3C (cementite) γ +L γ 1148°C (austenite) Fe3C (cementite) γ +L γ 1200 1148°C (austenite) 16 .8 g 600 400 0 1 2 3 α + Fe3C 4 5 6 Cα C Cγ O 6.2 g proeutectoid α = 48.7 3C Chapter 9 – Phase Equilibria c.7 − 0.7 g α = 94. the amount of pearlite and proeutectoid ferrite (α) note: amount of pearlite = amount of γ just above TE Co = 0. wt% C Chapter 9 .022 wt% C CFe C = 6.3 g 1000 800 727°C γ + Fe3C R S 600 400 0 1 2 3 α + Fe3C 4 5 6 Cα CO Co .022 wt% C Cpearlite = Cγ = 0. wt% C Chapter 9 .7g = 6.2 g γ + α Cγ − Cα 1600 δ T(°C) 1400 L L+Fe3C 1200 1000 800 γ + Fe3C 727°C RS pearlite = 51.76 wt% C γ C − Cα = o x 100 = 51.022 x 100 = 5.7 Co .

127.Callister 7e. 127. p. 1939. 9.) Chapter 9 . 1939. (Fig. % of alloying elements Adapted from Fig. Bain. --and the composition of each phase for a given T and composition of the system. Functions of the Alloying Elements in Steel. American Society for Metals.33 Summary • Phase diagrams are useful tools to determine: --the number and types of phases.34. p. 9. --the wt% of each phase. 9.Alloying Steel with More Elements • Teutectoid changes: T Eutectoid (°C) Ti Mo Si W Cr Mn Ni • Ceutectoid changes: C eutectoid (wt%C) Ni Cr Si Ti Mo W Mn wt.34 17 .Callister 7e. Functions of the Alloying Elements in Steel.) wt. 9. Bain.35. • Binary eutectics and binary eutectoids allow for a range of microstructures. (Fig. • Alloying to produce a solid solution usually --increases the tensile strength (TS) --decreases the ductility. Chapter 9 .35 from Edgar C. % of alloying elements Adapted from Fig. American Society for Metals.34 from Edgar C.

35 18 .ANNOUNCEMENTS Reading: Core Problems: Self-help Problems: Chapter 9 .