Phase diagrams.



Components and phases
• Each material can be characterized by it’s elemental composition and by it’s phase content. Phase content defines the structure of the material. Structure of the material determines it’s properties.
:Example :Phase content

Compositio n of the alloy 79.1 wt% Silver – 20.9 wt% Copper

β (lighter phase) Ag α (darker phase) Cu


• Phase is a homogeneous portion of a system that has specific atomic structure, physical and chemical characteristics. If more than one phase is present in a given system, each phase will have its own distinct properties and a boundary separating the phases.

Phase content depends on T & Composition (co) of the material. . Phase diagram represents this dependence • Changing T can change # of phases: path A to B • Changing Co can change # of phases: path B to C



Types of solid phases.
1) Solid solutions:

Interstitial Solid Solution: atoms with a small atomic radii dissolve in the lattice (they occupy interstitial positions). Usually interstitial atoms are: N, C, H, B. In such solution there is a limit of a 5 solubility.

Superlattice: solute atoms occupy only particular positions in the lattice, creating additional order – superlattice. These phases called – ordered phases.

Substitutional Solid Solution: in this solid solution solute atoms substitute the solvent atoms on random positions. Limit of solubility in such case depends on several conditions (Hume – Rothery rules).

When only a some maximum amount of a solute can be dissolved in a solvent. Limited solubility .When the amount of solute that can be dissolved in a solvent without creating a second phase is unlimited.   6 .Solubility Solubility . Unlimited solubility .The amount of one component (solute) that can be completely dissolved in a second component (solvent) without creating a second phase. The solublity is the main characteristic of solid solution. This amount is called “solubility limit”.

Thomson Learning™ is a trademark used herein under license. (b) Water and alcohol have unlimited solubility. (c) Salt and water have limited solubility. a division of Thomson Learning. Inc. Illustration: (a) Water exists in three states (phases): gas.©2003 Brooks/Cole. liquid. 7 . and solid. (d) Oil and water have no solubility.

solubility limit = 10wt% Sn..g. 8 . T α α + β • Ex: Phase Diagram: Pb-Sn System Question: What is the solubility limit of Sn in Pb at 100°C? 5 wt% Sn Answer: 5 wt% Sn.:Example of the Solubility Limit • Solubility Limit: Max concentration for which only a solution occurs. If Comp < 5 wt% Sn: α (Pb) If Comp > 5 wt% Sn: α (Pb) + β (Sn) coexist • Solubility limit increases with T: e. if T = 150°C.

Crystal structure factor – if the crystal structure of the two components is identical. .Hume-Rothery rules for solid solubility: . . solubility will be higher. the solubility is limited (due to high level of distortions in the lattice).Size factor – when the difference between the atomic diameter of the solvent and the solute atoms is more than 15%.Electronegativity factor – if solute and solvent stand close in the line of the 9 . .Valence factor – atoms with higher valence (those atoms that contribute more electrons) usually dissolve better than those atoms that have lower valence (atoms that contribute less electrons).

• rat Pb =3. ZCu =29. These elements stand very close in the periodical table: ZNi =28.243Å. Sn has tetragonal structure. Pb has FCC structure. rat Sn =2.278Å. ZSn =50. . ZPb =82. both have FCC structure.5Å.81Å. rat Ni =1.:Examples • rat Cu =1. both stand in the IV 10 column in the periodical table.

Phase is stable if it’s structure and characteristics do not change with time. • Equilibrium is best described in terms of a thermodynamic quantity called the free energy (G). Free energy is a function of the internal energy of a system and also function of the entropy of the system (the degree of randomness or disorder of the atoms in the structure). :Examples G At a specific T Phase with wide range of stability 11 G Intermetallic phase with narrow range of stability %C in wt %C in wt . A system is at equilibrium if its free energy is at a minimum under some specified combination of T (temperature). P (pressure) and C (composition).Phase equilibria • Phases can be stable (in equilibrium state) or metastable (non equilibrium).

12 .  Solidus temperature .The temperature below which all liquid has completely solidified.  Liquidus temperature .A phase diagram in which components display unlimited solid solubility.Definitions:  Binary phase diagram .The temperature at which the first solid begins to form during solidification.  Isomorphous phase diagram .A phase diagram for a system with two components.  Ternary phase diagram .A phase diagram for a system with three components.

Examples of binary :phase diagrams b) Peritectic phase diagram c) Complex phase diagram b Solid solution a a) Isomorphous phase diagram 13 c .

•Usually these diagrams are presented at constant pressure and at constant temperature. 14 . Image on the right present U-Fe-Al phase diagram at 850°C.:Ternary Phase Diagrams •Phase diagrams are also constructed for systems with more than 2 components.

Thomson Learning™ is a trademark used herein under license. 15 • Hypothetical ternary phase diagram presented on the left. . a division of Thomson Learning.(c)2003 Brooks/Cole. Inc.

their proportions. 16 .) In phase diagrams solubility limits are clearly seen.:Binary Phase Diagrams • Binary phase diagrams represent the relationships between temperature and compositions. showing the phases existing at equilibrium. and the manner in which they are distributed or arranged. In metal alloys. • Microstructure is subject of direct microscopic observations. (Pressure is held constant – normally 1 atm. microstructure is characterized by the phases present. using optical or electron microscopes. • Changes in the phases existing in the alloy and/or phase quantity will influence the microstructure of an alloy.

c) Mg2Pb is an intermediate phase.27Å. 17 .) c b b) Solid solution range of B in A is wider than solid solution range of A in B.24Å. (rat Cu =1.Solid solution a a) Cu and Ni are mutually soluble in each other in the solid state for all compositions. both FCC. same valence and close electronegativities. rat Ni =1. Existence of valence compound shortens the range of solid solution.

18 back2 .• This SEM image shows the lamellar eutectic structure in the alloy Al77wt%-Cu33wt%. The interlamellar spacing is about one micron.

19 . for metal-metal systems they are called intermetallic compounds (bonded by metallic bonds).:Intermediate Phases • For some systems intermediate compounds rather than solid solutions may be found on the phase diagram and these compounds have distinct chemical formulas and crystal structures.

. • Valence compounds are bonded by ionic or covalent bonds. • Valence compounds are brittle and have poor electrical 20 conductivity.Intermediate Phases: a) Valence Compounds • Valence compounds are created when the two components stands far away from each other in the periodical table. • Valence compounds can be either strictly stoichiometric (Mg2Pb previously) or to have some range of stability (γ and δ on the figure).

21 .74Å. Hägg. they have high hardness and high melting temperature.B.77Å. interstitial compounds are created: Fe3C. M4X or MX2. • According to G. MnN (ratC=0. M2X. TiN. • These compounds are very stable. R composition of interstitial compounds is: MX. • Homogeneity range of interstitial compounds can be quite wide. TaC.Intermediate Phases: b) Interstitial Compounds • When concentration of interstitial atoms (C.80Å).59 . when r < 0. ratN=0. WC.N) is more than solubility limit. ratB=0.

e. 22 --binary i.e... complete solubility of one Cu Ni .Binary Isomorphous Phase :Diagram F T>1453° F T=1290° F Cs CL liquid T<1085° solid • System is: component in another. α phase field extends from 0 to 100wt% Ni. 2 components: Cu and Ni. --isomorphous i.

The cooling curve for an isomorphous alloy during solidification T 1453 time T 1085 time 23 .

The cooling curve for an isomorphous alloy during solidification.©2003 Brooks/Cole. Inc. in this case for a Cu24 40% Ni alloy. We assume that cooling rates are small so as to allow thermal equilibrium to take place. Thomson Learning™ is a trademark used herein under license. The changes in slope of the cooling curve indicate the liquidus and solidus temperatures. a division of Thomson Learning. .

25 . 3) the percentage or fractions of the phases.Tie line CL CS For known composition and temperature at least 3 kinds of information are available: 1) the phases that are present. 2) the composition of these phases (according to the left and right points of the tie line).

:Lever Rule ©2003 Brooks/Cole. Cs – concentration of solid phase CL – concentration of liquid phase. Inc. a division of Thomson Learning. c0 • • • • • C0 – initial concentration of the component in the alloy. Thomson Learning™ is a trademark used herein under license. ML=weight of the liquid phase Ms=weight of the solid phase cLML+csMs=c0(ML+Ms) (cL-c0)ML+(cs-c0)Ms=0 M L cS − c0 = M S c0 − cL cS − c0 ML = cS − c L Lever rule ‫חוק מנוף‬ 26 c0 − cL MS = cS − c L .

• Equilibrium cooling 27 .Microstructures developed during equilibrium :cooling Zoom in of the area in the red square • Consider Co = 35wt%Ni.

• Cu-Ni case: Last α to solidify has Cα = 35wt%Ni. First α to solidify has C0 = 46wt%Ni. • Fast rate of • Slow rate of cooling: cooling: Cored structure First α to solidfy: 46wt%Ni Last α to solidfy: < 35wt%Ni Equilibrium structure Uniform Cα: 35wt%Ni 28 .:Non-Equilibrium Cooling • C changes during solidification process.

Usually eutectic exhibits lamellar microstructure.Binary Eutectic Phase Diagram Eutectic: is a specific mixture of two phases that simultaneously crystallize from molten solution at specific concentration and at specific temperature. which is the lowest temperature of crystallization /melting (Greek “eutektos”.meaning “easily melted”). Eutectic alloy – the mixture freezes as one at a single temperature When an alloy of non eutectic composition freezes one phase crystallizes at one temperature and the other phase crystallizes at a different temperature 29 .

Example of Binary Eutectic :Phase Diagram • Point E called eutectic point and it is an invariant point. this reaction may be written as following L→α +β 30 . which is designated by the composition ce and temperature Te. • Eutectic reaction occurs upon cooling the liquid with composition ce as it changes temperature in passing through Te.

:Cooling curves for eutectic diagram T b c Cooling curve of alloy with composition C: 779°C time Cooling curve of alloy with composition b: T 920 779 Cooling curve of pure component Cu T 1090 31 time Compare with Cooling curves for isomorphous alloys time .

T1 Relation between free energy curves of each phase and phase :diagram T2 T3 T3 T2 32 T1 .

:The microstructure developed in eutectic binary system 33 .

The microstructure is composed of a primary Pb rich (α prime) (large dark regions) within a lamelar eutectic structure consisting of a Sn rich β phase (light layers) and a Pb rich (α phase) (dark layers.Photomicrograph of PbSn alloy with 50wt%Pb. 34 .)X400.

wt% Sn eutectic 61.8 Co Co 200 TE 100 L +β β (Pb-Sn System) 0 0 Co.:Hypoeutectic & Hypereutectic alloys T(°C) 300 L α L +α α +β hypoeutectichypereutectic 20 18.3 40 60 80 100 97.9 hypoeutectic: C =50wt%Sn o hypereutectic: (illustration only) α α α α α α 175µm eutectic: C =61.9wt%Sn o β β 160µm β β β β eutectic micro-constituent 35 .

Calculation of amount of phases in the :eutectic systems Mβ In eutectic: M α = cβ − cE cE − cα C0 • Inside the eutectic structure: cβ − c E %α = cβ − cα CE Cβ Cα • If c0 is the initial concentration: cE − c0 %α prime = cE − cα 36 c0 − cα %eutectic = cE − cα .

37 . primary α is formed (green particles).:Binary Peritectic Systems C0 α L Peritectic reaction: L+α →β L β Upon cooling from the liquid phase. β phase is the product of the peritectic reaction between α and liquid. The β phase grows as sheath around the particles of the α phase.

• The peritectic reaction rarely goes to completion. since the formation of η around the e phase separates it from the liquid and inhibits further growth.e peritectic point e phase Liquid eutectic point η phase Sn η • This microstructure is obtained via a peritectic reaction (L+e → η ) in 21%wt Cu. . the remaining liquid transforms by a eutectic reaction to η 38 and Sn. Eventually.61%wt Sn alloy.

39 . eutectic reactions and melting of an alloy that belongs to an isomorphous system represent incongruent transformations.:Congruent Phase Transformations Those transformations for which all phases concerned have the same composition throughout the transformation are called congruent transformations. peritectic. For incongruent transformations. Examples: melting of pure materials and melting of the γ phase on the left image – are congruent. at least one of the phases will experience a change in composition.

Degree of freedom is a number of thermodynamic free variables (composition. where P-number of phases present. It defines the relationship between number of degrees of freedom and number of phases and number of components. temperature). temperature is the only variable which is noncompositional). pressure.g.:The Gibbs Phase Rule • Gibbs phase rule represents a criterion for the number of phases that coexist within a system at equillibrium. pressure) which can be changed. When pressure is constant: • F=C+1-P (since N=1.g. Cnumber of components in the system (example 2 for binary system). temperature. N-number of noncompositional variables (e. F-number of degrees of freedom or the number of externally controlled variables (e. temperature. pressure. composition). • P+F=C+N. 40 .

(These points are called triple points or invariant points. Eutectic and peritectic points are examples of such points.:Short summary For each phase diagram: • Tie lines on the diagram give the compositions of the phases in a two-phase field. • Gibbs phase rule applies. and their compositions are fixed.) 41 . three phases can only co-exist at a fixed temperature. For example: in binary systems at a constant pressure. • The lever rule applies to find the amount of each phase.

Fe-C Phase Diagram :Pure Iron Upon heating pure iron experiences 2 changes in crystal structure: At room temperature it exists as ferrite (Fe-α . 42 .BCC structure) At 912°C a polymorphic transformation occurs: ferrite → austenite (Fe-γ .FCC structure) At 1394°C austenite transforms to a BCC phase called δ ferrite.

Part of the Fe-C phase diagram .3% C – L  γ + Fe3C – (L  solid + solid) • Eutectoid: 0.8% C – γ  α + Fe3C – (solid  solid + solid) 43 .7% C cementite (Fe3C) Eutectic: 4.:Iron-Carbon (Fe-C) Phase Diagram • Pure iron: 3 solid phases – BCC ferrite (α ) – FCC Austenite (γ ) – BCC δ • • Beyond 6.

% C .Fe 44 wt.

direction of carbon diffusion indicated by arrows 45 . Pearlite microstructure: Just below the eutectoid point Schematic representation of the formation of pearlite from austenite.Fe-C Phase Diagram: Eutectoid Point Schematic representation of the microstructures for an iron-carbon alloy of eutectoid composition above and below the eutectoid temperature.

02) = 88% WFe3C = (0.02)/(6.8)/(6.Eutectoid Point: calculations • Just below the eutectoid point: Wα = (6.8- = 12% • • 46 .7-0.

:Hypoeutectoid Steel Proeutectoid α (α prim ): e α phase formed at T > Teutectoid 47 .

µ m 10 48 This is the image of two-phase structure (alpha-Fe + Pearlite) formed in Fe-0.4wt%C alloy .

:Hypereutectoid Steel 49 .

the dark phase is a ferrite phase. The majority of the area being taken by the pearlite eutectoid.• 50 Steel : Fe-1wt%C This secondary electron SEM image shows the cementite delineating prior austenite grain boundaries with a thin layer. . Each pearlite cell has a different orientation.

Example: calculations of the amounts according to lever rule 51 .

52 .

53 .

4 0.:Steel With Alloying Elements C eutectoid (wt%C) • Teutectoid T Eutectoid (°C) 1200 1000 800 600 0 Ni 4 Ti changes: Mo Si Cr Mn 8 12 W • Ceutectoid 0. % of alloying elements wt.2 0 0 changes: Ni Cr Si W 8 Mn 12 Ti Mo 4 wt. % of alloying elements 54 .8 0.6 0.

Example: stainless steel. At first. let us review Fe-Ni and Fe-Cr binary phase diagrams: Fe 55 .

additions of carbon help stabilize the austenite and therefore increase this limit.5 wt% chromium. 56 . the limit beyond which austenite no longer forms is about 13.Vertical section of Fe-Cr-C %.1C wt • This figure shows that an excessive amount of chromium can eliminate austenite at all temperatures. diagram for 0. However. • Without carbon. making it impossible to achieve a γ to α transition.

Inc. 57 . a division of Thomson Learning. The effect of 6% manganese on the stability ranges of the phases in the eutectoid portion of the Fe-Fe3C phase diagram. Thomson Learning™ is a trademark used herein under license.©2003 Brooks/Cole.

:Summary Make sure you understand language and concepts: • • • • • • • • • • • • Austenite Cementite Component Congruent transformation Equilibrium Eutectic phase/reaction/structure Eutectoid reaction Ferrite Hypereutectoid alloy Hypoeutectoid alloy Intermetallic compound Isomorphous •Lever rule •Liquidus line •Metastable •Microstructure •Pearlite •Peritectic reaction •Phase •Phase diagram •Primary phase •Solidus line •Solubility limit •System •Tie line 58 .

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