CHAPTER

8
Phase Diagrams
8-1

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Introduccin
Fase: Una region en un material que difiere en estructura y funcin de otra regin. Diagramas de fase :
Representan las fases presentes en el metal a diferentes condiciones (Temperatura, presin y composicin). Indica la solubilidad de un slido en equilibrio en otro elemento. Indica el rango de temperatura en el cual ocurre la solidificacin. Indica la temperatura a la cual las diferentes fases inician su fusin.

8-2

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Diagram de fase de substancias puras Las sustancias puras existen en estado slido, lquido y vapor. Las fases estan separadas por lmites de fase Ejemplo : Agua, Hierro puro.

Figure 8.1

Figure 8.2

Diferentes fases coexisten en el punto triple.

8-3
After W. G. Moffatt, et al., The Structure and Properties of Materials, vol I: Structure, Wiley, 1965, p.151

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

REGLA DE LAS FASES DE GIBBS

P+F = C+2 P = nmero de fase que coexisten en un sistema C = Numero de componentes F = Grados de libertad Para el agua pura, en el punto triple, coexisten 3 fases. Hay un componente (agua) en el sistema. As que 3 + F = 1 + 2 F = 0. Los grados de libertad indican el nmero de variable que pueden ser cambiadas sin que cambie el nmero de fases.

8-4

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Curvas de enfriamiento en equilibrio Usedas para determinar la temperatura de transicin de la fase.

Pure Metal Iron

Meseta trmica : prdida de calor = calor necesario para solidifacar el metal. Las aleaciones solidifican en un rango de temperatura (sin meseta trmica)

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Sistema de aleacin Binario Isomorfo

Aleacin binaria Sistema de dos componentes

Sistema Isomorfo : Los dos elementos son completamente solubles en estado lquido y en estado slido. Ejemplo: CuNi solucin.
La Composicin de las fases puede ser determinada A cualquier temperatura en forma grfica.

Figure 8.3 8-5

Adapted from Metals Handbook, vol. 8, 8th ed., American society of Metals, 1973, p. 294.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Phase Diagram from Cooling Curves

Series of cooling curves at different metal composition are first constructed. Points of change of slope of cooling curves (thermal arrests) are noted and phase diagram is constructed. More the number of cooling curves, more accurate is the phase diagram.

Figure 8.4 8-6

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

The Lever Rule

The Lever rule gives the weight % of phases in any two phase regions. Wt fraction of solid phase = Xs = w0 w1 ws w1 Wt fraction of liquid phase = X1 = ws w0 ws w1

Figure 8.5 8-7

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Non Equilibrium Solidification of Alloys

Very slow cooling (equilibrium) gives rise to cored structure. Rapid cooling delays solidification.
Homogenization: Cast ingots heated to elevated temperature to eliminate cored structure. Temperature of homogenization must be lower than lowest melting point of any of the alloy components.

Figure 8.7 8-8

Figure 8.8

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Binary Eutectic Alloy System

In some binary alloy systems, components have limited solid solubility. Example : Pb-Sn alloy. Eutectic composition freezes at lower temperature than all other compositions. This lowest temperature is called eutectic temperature.

Figure 8.11 Eutectic temperature

Liquid
8-9

Cooling

solid solution + solid solution

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Slow Cooling of 60% Pb 40% Sn alloy

Liquid at 3000C. At about 2450C first solid forms proeutectic solid. 0C Slightly above 183 Figure 8.12 composition of alpha follows solidus and composition of sn varies from 40% to 61.9%. At eutectic temperature, all the remaining liquid solidifies.

Figure 8.13

Further cooling lowers alpha Sn content and beta Pb.

8-10
From J. Nutting and R. G. Baker, Microstructure of Metals, Institute of Metals, London, 1965,p.19.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Various Eutectic Structures

Structure depends on factors like minimization of free energy at / interface. Manner in which two phases nucleate and grow also affects structures.

Figure 8.14 8-11

After W. C. Winegard, An Introduction to the Solidification of Metals, Institute of Metals, London, 1964.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Binary Peritectic Alloy System

Peritectic reaction: Liquid phase reacts with a solid phase to form a new and different solid phase. Liquid +
cooling

Peritectic reaction occurs when a slowly cooled alloy of Fe-4.3 wt% Ni passes through Peritectic temperature of 15170C. Peritectic point is invariant.
Figure 8.16

Liquid(5.4 wt% Ni) + (4.0 wt% Ni)

8-12

cooling

4.3 wt % Ni

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Peritectic Alloy System

At 42.4 % Ag & 14000C Phases present Liquid Alpha Composition 55% Ag 7%Ag Amount of Phases 42.4 7 55-42.4 55 7 55 - 7 = 74% = 26% At 42.4% Ag and 11860C T Phase Present Beta only Composition 42.4% Ag Amount of Phase 100% At 42.4% Ag and 11860C + T Phases present Liquid Alpha Composition 66.3% Ag 10.5%Ag Amount of Phases 42.4 10.5 66.3-42.4 66.3 10.5 66.310.5 = 57% =43%

Figure 8.17

Figure 8.18

8-13

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Rapid Solidification in Peritectic System

Surrounding or Encasement: During peritectic reaction, L+ , the beta phase created surrounds primary alpha. Beta creates diffusion barrier resulting in coring.

Figure 8.19 Figure 8.20 8-14

After F Rhines, Phase Diagrams in Metallurgy,McGraw- Hill, 1956, p. 86.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Binary Monotectic Systems

Monotectic Reaction: Liquid phase transforms into solid phase and another liquid. L1 Cooling + L2 Two liquids are immiscible. Example:- Copper Lead system at 9550C and 36% Pb.
Table 8.1

Eutectic Eutectoid Peritectic Peritectoid Monotectic

Figure 8.23 8-15

Metals Handbook, vol. 8: Metallography Structures and Phase Diagrams, 8th ed., American Society of Metals, 1973, p. 296.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Intermediate Phases and Compounds

Terminal phases: Phases occur at the end of phase diagrams. Intermediate phases: Phases occur in a composition range inside phase diagram. Examples: Cu-Zn diagram has both terminal and intermediate phases. Five invariant peritectic points and one eutectic point.
Figure 8.25 8-16 Metals Handbook, vol. 8: Metallography Structures and Phase Diagrams, 8th ed., American Society of Metals, 1973, p. 301

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Intermediate Phases in Ceramics

In Al2O2 SiO2 system, an intermediate phase called Mullite is formed, which includes the compound 3Al2O3.2SiO2.

Figure 8.26 8-17

After A. G. Guy, Essentials of Materials Science, McGraw-Hill, 1976

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Intermediate Compounds
In some phase diagrams, intermediate compound are formed Stoichiometric Percent Ionic/Covalent bond depends on electronegativeness Example:- Mg-Ni phase diagram contains
Mg2Ni : Congruently melting compound MgNi2 : Incongruently melting compound.

Figure 8.27 8-18

Metals Handbook, vol. 8: American Society of Metals, 1973, p. 314.

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Ternary Phase Diagrams

Three components Constructed by using a equilateral triangle as base. Pure components at each end of triangle. Binary alloy composition represented on edges.

Figure 8.28

Temperature can be represented as uniform throughout the Whole Diagram Isothermal section.
8-19

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display

Ternary Phase Diagram (Cont..)

Example:- Iron-Chromium-Nickel phase diagrams. Isothermal reaction at 6500C for this system Composition of any metal at any point on the phase diagram can be found by drawing perpendicular from pure metal corner to apposite side and calculating the % length of line at that point
Figure 8.30 8-20
After Metals Handbook, vol. 8: American Society of Metals, 1973, p. 425.