Phase Diagrams Equilibrium Microstructural Development

CHAPTER

The microstructure of a slowly cooled eutectic soft solder ( 38 wt % Pb wt % Sn) consists of a lamellar structure of tin-rich solid solution (white) and lead-rich solid solution (dark), 375X. (From ASM Handbook, Vol. 3: Alloy Phase Diagrams, ASM International, Materials Park, Ohio, 1992.)

Figure 9-1 Single-phase microstructure of commercially pure molybdenum, 200 . Although there are many grains in this microstructure, each grain has the same, uniform composition. (From Metals Handbook, 8th ed., Vol. 7: Atlas of Microstructures, American Society for Metals, Metals Park, Ohio, 1972.)

Figure 9-2 Two-phase microstructure of pearlite found in a steel with 0.8 wt % C, 500 . This carbon content is an average of the carbon content in each of the alternating layers of ferrite (with < 0.02 wt % C) and cementite (a compound, Fe 3 C, which contains 6.7 wt % C). The narrower layers are the cementite phase. (From Metals Handbook, 9th ed., Vol. 9: Metallography and Microstructures, American Society for Metals, Metals Park, Ohio, 1985.)

Temperature

Gas

T ( C) 100

Steam

Liquid 0 Solid 1 atm (a) Pressure (log scale) (b)

Water

Ice

Figure 9-3 (a) Schematic representation of the one-component phase diagram for H 2 O. (b) A projection of the phase diagram information at 1 atm generates a temperature scale labeled with the familiar transformation temperatures for H 2 O (melting at 0 C and boiling at 100 C).

Temperature Gas Liquid

T(C) Liquid 1538 1394 910

1 atm Pressure (log scale) (a)

(b)

Figure 9-4 (a) Schematic representation of the one-component phase diagram for pure iron. (b) A projection of the phase diagram information at 1 atm generates a temperature scale labeled with important transformation temperatures for iron. This projection will become one end of important binary diagrams such as Figure 919.

Liquidus L

Melting point of B

Temperature

L + SS Melting point of A

Solidus SS

A 0 100

20 80

40 60

60 40

80 20

B 100 wt % B 0 wt % A

Composition (wt %)
Figure 9-5 Binary phase diagram showing complete solid solution. The liquidphase eld is labeled L and the solid solution is designated SS. Note the two-phase region labeled L + SS.

Composition of L at T1 L System temperature T1 L + SS

State point

Composition of SS at T1

SS

X1 System composition

Figure 9-6 The compositions of the phases in a two-phase region of the phase diagram are determined by a tie line (the horizontal line connecting the phase compositions at the system temperature).

Temperature

F=CP+1 F =21+1=2 F =12+1=0

F =22+1 =1

F =21+1=2

A Composition

Figure 9-7 Application of Gibbs phase rule (Equation 9.2) to various points in the phase diagram of Figure 95.

Temperature

Lsystem

All liquid (Lsystem)

T1

L1

Crystallites of SS1 in matrix of L1 SS1 Polycrystalline solid (SSsystem) SSsystem

A System composition Composition

Figure 9-8 Various microstructures characteristic of different regions in the complete solid-solution phase diagram.

C 1500 1400 1300 1200 1100 1000 900 800 700 600 500 Cu

Atomic percentage nickel 10 20 30 L 40 50 60 70 80 90 1455

1084.87

10

20

40 30 50 60 70 Weight percentage nickel

80

90

Ni

Figure 9-9 CuNi phase diagram. (After Metals Handbook, 8th ed., Vol. 8: Metallography, Structures, and Phase Diagrams, American Society for Metals, Metals Park, Ohio, 1973, and Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

C 2800 L 2600 2400 2200 2000 NiO 20 40 60 80 MgO Mole % MgO

Figure 9-10 NiOMgO phase diagram. (After Phase Diagrams for Ceramists, Vol. 1, American Ceramic Society, Columbus, Ohio, 1964.)

L + SS SS

Temperature

Liquidus A+L Solidus A+B A Eutectic Composition

L+B

Eutectic temperature

B Composition

Figure 9-11 Binary eutectic phase diagram showing no solid solution. This general appearance can be contrasted to the opposite case of complete solid solution illustrated in Figure 95.

Temperature All liquid (Leutectic)

Crystallites of A in matrix of L1

L1 L2 Leutectic

Crystallites of B in matrix of L2

Eutectic microstructure fine, alternating layers of A and B

A Composition

Figure 9-12 Various microstructures characteristic of different regions in a binary eutectic phase diagram with no solid solution.

C 1500 1400 1300

Atomic percentage, silicon 10 20 30 40 50 60 70 80 90 1414

L 1200 1100 1000 900 800 700 600 1.6 500 400 300 A1 12.6

660.452 577

10

20

30

40

50

60

70

80

90

Si

Weight percentage, silicon

Figure 9-13 AlSi phase diagram. (After Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

Temperature
A Composition
Figure 9-14 Binary eutectic phase diagram with limited solid solution. The only difference from Figure 911 is the presence of solid-solution regions and .

Temperature All liquid (Leutectic) Leutectic L1 L2

A Composition

Figure 9-15 Various microstructures characteristic of different regions in the binary eutectic phase diagram with limited solid solution. This illustration is essentially equivalent to Figure 912 except that the solid phases are now solid solutions ( and ) rather than pure components (A and B).

Atomic percentage tin C 400 300 200 100 0 Pb 13 10 20 30 40 50 60 Weight percentage tin 70 80 90 Sn 10 20 30 40 50 60 70 L 231.9681 19 183 61.9 97.5 80 90

327.502

Figure 9-16 PbSn phase diagram. (After Metals Handbook, 8th ed., Vol. 8: Metallography, Structures, and Phase Diagrams, American Society for Metals, Metals Park, Ohio, 1973, and Binary Alloy Phase Diagrams, Vol. 2, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

Temperature L

Eutectic temperature Eutectoid temperature

A Eutectoid composition Eutectic composition

Composition
Figure 9-17 This eutectoid phase diagram contains both a eutectic reaction (Equation 9.3) and its solid-state analog, a eutectoid reaction (Equation 9.4).

Temperature

A Composition

Figure 9-18 Representative microstructures for the eutectoid diagram of Figure 917.

C 1700

Atomic percentage carbon 10 15 20

25

1600 1538 1500 1400 1300 1200 1100 1000 900 912 800 700 600 500 400 300 200 100 0 Fe

1495

1394 1227C 1148 2.11 4.30 L + Fe3C 6.69

727 0.02 0.77 Fe3C (cementite)

Weight percentage carbon

Figure 9-19 FeFe 3 C phase diagram. Note that the composition axis is given in weight percent carbon even though Fe 3 C, and not carbon, is a component. (After Metals Handbook, 8th ed., Vol. 8: Metallography, Structures, and Phase Diagrams, American Society for Metals, Metals Park, Ohio, 1973, and Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

C 2200 2100 2000 1900 1800 1700 1600 1500 1400 1300 1200 1100 1000 900 800 700 600 500 400 300 200 100 0 Fe

Atomic percentage carbon 10 15 20

25

1538

1495

L+C

1394 1154 2.08 912 738 0.02 0.68 C (graphite) 4.26

3 4 5 6 Weight percentage carbon

99

100

Figure 9-20 FeC phase diagram. The left side of this diagram is nearly identical to that for the FeFe 3 C diagram (Figure 919). In this case, however, the intermediate compound Fe 3 C does not exist. (After Metals Handbook, 8th ed., Vol. 8: Metallography, Structures, and Phase Diagrams, American Society for Metals, Metals Park, Ohio, 1973, and Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

Temperature Composition of liquid formed upon melting of AB L L+B

A + L L + AB A + AB

AB + B

AB Composition

Figure 9-21 Peritectic phase diagram showing a peritectic reaction (Equation 9.5). For simplicity, no solid solution is shown.

Temperature

Crystallites of B in matrix of L1 L Polycrystalline solid (compound AB)

AB Composition

Figure 9-22 Representative microstructures for the peritectic diagram of Figure 921.

C 2200 2100 2000 L + Al2O3 1900 1800 1700 1600 1500 1400 SiO2 SiO2 (cristobalite) + L 1890

2054

1726

L + mullite(SS) Al2O3 + mullite(SS) 1587 SiO2 (cristobalite) + mullite(SS) 10 20 30 40 50 Mole % Al2O3

mullite(SS)

60

70

80

90

Al2O3

Figure 9-23 Al 2 O 3 SiO 2 phase diagram. Mullite is an intermediate compound with ideal stoichiometry 3Al 2 O 3 2SiO 2 . (After F. J. Klug, S. Prochazka, and R. H. Doremus, J. Am. Ceram. Soc. 70, 750 (1987).)

Figure 9-24 (a) Binary phase diagram with a congruently melting intermediate compound, AB. This diagram is equivalent to two simple binary eutectic diagrams (the AAB and ABB systems). (b) For analysis of microstructure for an overall composition in the AB B system, only that binary eutectic diagram need be considered.

Temperature

A+L

AB + L L + AB

B+L

A + AB A AB

AB + B B

Composition (a)

Temperature

A+L

AB + L L + AB

B+L

A + AB A AB

AB + B B

Composition (b)

Temperature

A 2B

AB Composition (a)

AB2

AB4

Temperature

A 2B

AB Composition

AB2

AB4

C 3000

L 2500

L + spinel (SS) 2000 Periclase (SS) +L L + Al2O3

Periclase (SS)

Spinel (SS)

1500

Periclase (SS) + spinel (SS)

Spinal (SS) + Al2O3

1000 MgO

10

20

30

40

50

60

70

80

90

Al2O3

Mole % Al2O3

Figure 9-26 MgOAl 2 O 3 phase diagram. Spinel is an intermediate compound with ideal stoichiometry MgO Al 2 O 3 . (After Phase Diagrams for Ceramists, Vol. 1, American Ceramic Society, Columbus, Ohio, 1964.)

C 0 1100 1000 900 800 700 600

Atomic percentage, copper 10 20 30 40 50 60 70 80 90 100

1084.87

660.452 53.5 548.2 1 32.7 52.5 5.65 567

500 400 300 Al

10

20

30

40 50 60 Weight percentage, copper

70

80

90

Cu

Figure 9-27 AlCu phase diagram. (After Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

C 700 600 500 400 300 200 100 Al

Atomic percentage, magnesium 10 660.452 L 35.6 450 17.1 36.1 455 59.8 66.7 437 87.4

20

30

40

50

60

70

80

90

100 650

10

20

30 40 50 60 70 Weight percentage, magnesium

80

90

Mg

Figure 9-28 AlMg phase diagram. (After Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

Atomic percentage, zinc C 1300 1250 1200 1150 1100 1050 1000 950 900 850 800 750 700 650 600 550 500 450 400 350 300 250 200 150 100 50 0 Cu 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 Zn 99.7% at 100 39.0 456 48.9 45.5 468 87.5 424 97.3 419.58 74.1 78.6 598 558 98.3 69.8 73.0 700 80.5 32.5 903 36.8 56.5 59.8 835 37.5 1084.87 L 10 20 30 40 50 60 70 80 90

Atomic percentage Cu 1 2 3 450 L 1.7 424 400 350 300 250 200 150 100 1 Zn 2 3 Weight percentage Cu 2.7

Weight percentage, zinc

Figure 9-29 CuZn phase diagram. (After Metals Handbook, 8th ed., Vol. 8: Metallography, Structures, and Phase Diagrams, American Society for Metals, Metals Park, Ohio, 1973, and Binary Alloy Phase Diagrams, Vol. 1, T. B. Massalski, ed., American Society for Metals, Metals Park, Ohio, 1986.)

C 2500

CaO (wt %) 12 16

20

24

28

2000

Tetragonal ZrO2SS + Cubic ZrO2SS

Tetragonal ZrO2SS

1500

Cubic ZrO2SS

1000

Cubic ZrO2SS + ZrCaO3

500

0 ZrO2

Monoclinic ZrO2SS + Cubic ZrO2SS

10

20 30 CaO (mol %)

40

50

Figure 9-30 CaOZrO 2 phase diagram. The dashed lines represent tentative results. (After Phase Diagrams for Ceramists, Vol. 1, American Ceramic Society, Columbus, Ohio, 1964.)

Temperature

A2B

AB Composition

AB2

AB4

Temperature L L + SS T1

SS

0 A

30 50 80 100 Composition (wt % B) B mL + mSS = mtotal 0.30mL + 0.80mSS = 0.50mtotal mL = 0.60mtotal mSS = 0.40mtotal

Figure 9-31 A more quantitative treatment of the tie line introduced in Figure 96 allows the amount of each phase (L and SS) to be calculated by means of a mass balance (Equations 9.6 and 9.7).

(a)

Fulcrum

(b)

Figure 9-32 The lever rule is a mechanical analogy to the mass balance calculation. The (a) tie line in the two-phase region is analogous to (b) a lever balanced on a fulcrum.

Temperature

Lsystem

100% liquid (Lsystem) T1 T2 T3 L3 L2 SS2 SS3 40% SS2 in matrix of L2 L1 SS1 10% SS1 in matrix of L1

SSsystem

90% SS3 in matrix of L3

Composition

100% Solid (SSsystem)

Figure 9-33 Microstructural development during the slow cooling of a 50% A50% B composition in a phase diagram with complete solid solution. At each temperature, the amounts of the phases in the microstructure correspond to a lever rule calculation. The microstructure at T2 corresponds to the calculation in Figure 931.

Temperature Leutectic 100% liquid (Leutectic)

T1 T2 A Composition B

*The only differences from the T1 microstructure are the phase compositions and the relative amounts of each phase. For example, the amount of b will be proportional to

Figure 9-34 Microstructural development during the slow cooling of a eutectic composition.

Temperature Lsystem

100% liquid (Lsystem = 80% B)

L2 T2 (= Teutectic + 1 ) T3 (= Teutectic 1 )

L1

0 A

30 60 80 Composition (wt % B)

90 100 B

Figure 9-35 Microstructural development during the slow cooling of a hypereutectic composition.

Temperature 100% liquid (Lsystem = 40% B) Lsystem

L1 T2 (= Teutectic + 1 ) T3 (= Teutectic 1 )

0 A

30 40 60 Composition (wt % B)

90 100 B

Figure 9-36 Microstructural development during the slow cooling of a hypoeutectic composition.

Temperature Lsystem 100% liquid (Lsystem = 10% B) L1

0 A

10

Composition (wt % B) (a)

100 B

100% liquid (Lsystem = 20% B)uid (Lsystem = 20%

Lsystem

Temperature

L1

0 A

10

20

Composition (wt % B) (b)

100 B

Temperature 100% liquid (3% C)

L1

3.0 Weight percentage carbon

6.7

Figure 9-38 Microstructural development for white cast iron (of composition 3.0 wt % C) shown with the aid of the FeFe 3 C phase diagram. The resulting (low-temperature) sketch can be compared with a micrograph in Figure 111a.

Temperature

0.77 Weight percentage carbon

6.7

Figure 9-39 Microstructural development for eutectoid steel (of composition 0.77 wt % C). The resulting (low-temperature) sketch can be compared with the micrograph in Figure 92.

Temperature

Proeutectoid cementite + pearlite

1.13 Weight percentage carbon

6.7

Figure 9-40 Microstructural development for a slowly cooled hypereutectoid steel (of composition 1.13 wt % C).

Temperature

Proeutectoid ferrite + pearlite

0 0.50 Weight percentage carbon

6.7

Figure 9-41 Microstructural development for a slowly cooled hypoeutectoid steel (of composition 0.50 wt % C).

Temperature 100% liquid (3% C)

L1

C flakes (from eutectic and eutectoid reactions) in matrix of ferrite

3 Weight percentage carbon

100

Figure 9-42 Microstructural development for gray cast iron (of composition 3.0 wt % C) shown on the FeC phase diagram. The resulting low-temperature sketch can be compared with the micrograph in Figure 111b. A dramatic difference is that, in the actual microstructure, a substantial amount of metastable pearlite was formed at the eutectoid temperature. It is also interesting to compare this sketch with that for white cast iron in Figure 938. The small amount of silicon added to promote graphite precipitation is not shown in this two-component diagram.

The phase diagram for this alloy system is T