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    02 Phase Diagrams

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    Palash Swarnakar
    (1) Phase diagrams map the existence and equilibrium conditions of various phases in a system as temperature and pressure are varied. They show boundaries between solid, liquid, and gas phases. (2) Binary phase diagrams illustrate phase equilibria for systems with two components, such as alloys. Isomorphous systems form continuous solid solutions, while eutectic systems have a valley-shaped diagram with a eutectic point where solidification yields two solid phases. (3) Nonequilibrium solidification below the equilibrium cooling rate can lead to compositional variations within phases, known as coring, due to insufficient diffusion. Eutectic alloys are also more prone to nonequilibrium effects

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    02 Phase Diagrams

    Uploaded by

    Palash Swarnakar
    45 views24 pages
    (1) Phase diagrams map the existence and equilibrium conditions of various phases in a system as temperature and pressure are varied. They show boundaries between solid, liquid, and gas phases. (2) Binary phase diagrams illustrate phase equilibria for systems with two components, such as alloys. Isomorphous systems form continuous solid solutions, while eutectic systems have a valley-shaped diagram with a eutectic point where solidification yields two solid phases. (3) Nonequilibrium solidification below the equilibrium cooling rate can lead to compositional variations within phases, known as coring, due to insufficient diffusion. Eutectic alloys are also more prone to nonequilibrium effects

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    (1) Phase diagrams map the existence and equilibrium conditions of various phases in a system as temperature and pressure are varied. They show boundaries between solid, liquid, and gas phases. (2) Binary phase diagrams illustrate phase equilibria for systems with two components, such as alloys. Isomorphous systems form continuous solid solutions, while eutectic systems have a valley-shaped diagram with a eutectic point where solidification yields two solid phases. (3) Nonequilibrium solidification below the equilibrium cooling rate can lead to compositional variations within phases, known as coring, due to insufficient diffusion. Eutectic alloys are also more prone to nonequilibrium effects

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    45 views24 pages

    02 Phase Diagrams

    Uploaded by

    Palash Swarnakar
    (1) Phase diagrams map the existence and equilibrium conditions of various phases in a system as temperature and pressure are varied. They show boundaries between solid, liquid, and gas phases. (2) Binary phase diagrams illustrate phase equilibria for systems with two components, such as alloys. Isomorphous systems form continuous solid solutions, while eutectic systems have a valley-shaped diagram with a eutectic point where solidification yields two solid phases. (3) Nonequilibrium solidification below the equilibrium cooling rate can lead to compositional variations within phases, known as coring, due to insufficient diffusion. Eutectic alloys are also more prone to nonequilibrium effects

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
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    of 24

    Phase Diagrams a Review

    Topic 2

    Review of Phase Transformation Diagrams

    Solution and Solubility


    Example: Solubility of salt in water There exists a maximum amount of salt that can be completely dissolved in water; excess of salt stays as solid. This maximum amount is the solubility of salt in water. The solution containing the maximum concentration of salt is a saturated solution. Cooling of saturated solution results in the formation of solid salt from the solution, indicating that solubility decreases with decreasing T. This process is called precipitation and the solid formed is a precipitate. Solid salt the Heating the solution will lead to the dissolving of the precipitate precipitate back into solution. In this example there exist two phases in the system and the two phases stay in equilibrium: dissolving

    Salty water the solution

    Solution

    Solid

    precipitation

    The same concepts apply to solids: solid solution, saturation, solubility, precipitation

    Phase Diagrams
    phase diagram of water
    Phase diagrams are used to map out the existence and conditions of various phases of a give system. The phase diagram of water is a common example. Water may stay in liquid, solid or gaseous states in different pressure-temperature regions. Boundaries of the regions express the equilibrium conditions in terms of P and T. Water is a monolithic system. For binary systems, which contains two constituents, such as binary alloys, phase diagrams are often expressed in the temperature-composition plane.
    Liquid Solid Pressure
    221 bar 1 bar 0 bar

    Critical point

    Triple point
    0C

    Gas

    100C

    374C

    Temperature

    Super-critical fluid

    Binary Phase Diagrams


    Temperature
    The simplest type of binary phase diagrams is the isomorphous system, in which the two constituents form a continuous solid solution over the entire composition range. An example is the Ni-Cu system. Solidication of alloy Co starts on cooing at T1. The rst solid formed has a composition of Cs1 and the liquid Co. On further cooling the solid particles grow larger in size and change their composition to Cs2 and then Co, following the solidus whereas the liquid decrease in volume and changes its composition from Co to CL3 following the liquidus. The solidication completes at T3.
    liquid phase Solution of Cu and Ni

    1455C

    T1 T2 CL T3 CL 2 3 1085C

    Co CS Co 2

    CS 1

    phase (fcc) Solid solution of Cu and Ni

    Cu
    L

    Composition

    Ni

    Binary Phase Diagrams


    Temperature
    The simplest type of binary phase diagrams is the isomorphous system, in which the two constituents form a continuous solid solution over the entire composition range. An example is the Ni-Cu system. Compositions of phases is determined by the tie line The relative fractions of the phases are determined by the lever rule 1085C
    W1 W2 liquid phase Solution of Cu and Ni

    1455C Co

    T*

    CL

    CS

    phase (fcc) Solid solution of Cu and Ni

    L1

    L2

    Cu

    Composition

    Ni

    Lever Rule
    W1 W2

    L1

    L2

    Weight fractions:

    Example
    At temperature T1, alloy Co is in the dual phase region, comprising the liquid phase and the -phase. (i) Determine the compositions of the two phases; (ii) Determine the weight fractions of the two phases Read from the tie line: Liquid phase:Cu-30%Ni -phase: Cu-55%Ni 1455C C0 T1 CL CS
    CL Co CS

    WL =

    Cs Co 55 50 = = 0.2 = 20% Cs CL 55 30

    W = or

    Co CL 50 30 = = 0.8 = 80% Cs CL 55 30

    1085C 30%Ni Cu 50%Ni 55%Ni Ni

    W = 1 WL = 1 0.2 = 0.8 = 80%

    determination of Phase diagrams


    II T 1085C
    (thermal arrest)

    Cooling Curves
    Liquidus

    1455C T1
    Solidus

    T I T1 T T2 1085C II Cu t

    T2

    I %

    III Ni

    Eutectic Systems
    Pb-Sn phase diagram
    The Pb-Sn system is characteristic of a valley in the middle. Such system is known as the Eutectic system. The central point is the Eutectic point and the transformation though this point is called Eutectic reaction: L+ Pb has a fcc structure and Sn has a tetragonal structure. The system has three phases: L, and .
    350 300
    Liquidus Liquid

    Temperature

    250 200 150 100 50 0 +L


    solidus phase: solid solution of Sn in fcc Pb solvus

    Eutectic point

    L+
    phase: solid solution of Pb in tetragonal Sn solvus

    + 30 40 50 60 70

    0 10 Pb (Fcc)

    20

    80

    Wt%

    90 100 Sn (Tetra)

    Solidification of Eutectic Systems


    Pb-Sn phase diagram
    Alloy I: At point 1: Liquid Solidication starts at liquidus At point 2: L+ The amount with T Solidication nishes at solidus At point 3: Precipitation starts at solvus At point 4: + Further cooling leads to formation and growth of more precipitates whereas Sn% in decreases following the solvus. The cooling curve of this alloy is similar to cooling curve I shown in slide 9.
    350 300

    I
    1 2 3

    III

    II
    Liquid

    Temperature

    250 200 150 100 50 0

    0 10 Pb (Fcc)

    20

    30

    40

    50

    60

    70

    80

    Wt%

    90 100 Sn (Tetra)

    (1)

    L L

    (2)

    (a)

    L
    Precipitates in a Al-Si alloy; (a) optical microscopy, (b) scanning electron microscopy of fracture surface

    (3)

    (4)


    (b)

    Solidification of Eutectic Systems


    Alloy II: At point 1: Liquid Solidication starts at eutectic point (where liquidus and solidus join) At point 2: L(+) (eutectic reaction) The amounts of and increase in proportion with time. Solidication nishes at the same temperature. At point 3: + Further cooling leads to the depletion of Sn in and the depletion of Pb in . The cooling curve of this alloy is similar to cooling curve II shown in slide 9.

    Pb-Sn phase diagram


    350 300

    III

    II

    Liquid

    Temperature

    250 200 150 100 50 0

    0 10 Pb (Fcc)

    20

    30

    40

    50

    60

    70

    80

    Wt%

    90 100 Sn (Tetra)

    (1)

    L L

    (2)

    (3)

    Nucleation of colonies of and laminates

    Pb-Sn eutectic

    Eutectic structure of intimate mix of and to minimise diffusion path

    Solidification of Eutectic Systems


    Alloy III: At point 1: Liquid Solidication starts at liquidus At point 2: LL+ (pre-eutectic ) The amount with T At point 3: L (+) (eutectic reaction) Solidication nishes at the eutectic temperature At point 4: + (pre-eutectic + (+) eutectic mixture) Further cooling leads to the depletion of Sn in and the depletion of Pb in . The cooling curve of this alloy is a combination of the two cooling curves shown in slide 9.

    Pb-Sn phase diagram


    350 300

    I
    1

    III

    II

    Liquid

    Temperature

    250 200 150 100 50 0


    2 3 4

    0 10 Pb (Fcc)

    20

    30

    40

    50

    60

    70

    80

    Wt%

    90 100 Sn (Tetra)

    (1)

    L L

    (2)

    Cooling curve

    (3)

    (3)

    Pr e-

    Cu-Ag alloy
    eu tec tic

    Eut

    Eutectic laminate of and

    Solidification of Eutectic Systems


    350 300 Can you describe the solidication process of alloy IV, including microstructure evolution, morphology of phases and cooling curve? 250 200 150 100 50 0
    Pb Sn +

    III
    Liquid

    II

    IV

    Hypoeutectic

    Hypereutectic

    Gibbs Phase Rule


    Gibbs phase rule F =C+N-P F: degree of freedom C: number of chemical variables N: number of non-chemical variables P: number of phases Application of Gibbs phase rule: For a binary system at ambient pressure: C=2 (2 elements) N=1 (temperature, no pressure) For single phase: F=2: % and T (a region) For a 2-phase equilibrium: F=1: % or T (a line) For a 3-phase equilibrium: F=0, (invariant point) May we have a 4-phase equilibrium, in a binary system, or in any system?
    Pb

    one-phase region two-phase equilibrium (line)

    three-phase equilibrium (point)

    + Sn

    Non-Equilibrium Solidification
    Some transformations do not cause changes in composition, such as the solidication of a pure metal, whereas some other do, such as the solidication of an alloy into a solid solution. The former is known as congruent transformation and the latter incongruent transformations. Congruent transformations are cooling rate insensitive and incongruent transformations are cooling rate sensitive they rely on interdiffusion to proceed. Solidication under a fast cooling rate, where diffusion is insufcient to homogenise the composition simultaneously during the process is known as the non-equilibrium solidication. A common consequence of non-equilibrium solidication is coring.

    Coring
    Alloy Co starts solidication at T1. The rst solid formed has composition Cs1. On further cooling to T2, an outer shell of composition Cs2 is formed surrounding Cs1. Due to inadequate diffusion on fast cooling, a composition difference is created. The average composition of the solid composite at T2 is, thus, somewhere between Cs1 and Cs2: Cs2*. The same situation continues throughout the process. Under equilibrium condition solidication completes at T3. However, under nonequilibrium condition, the average composition of solid at T3 is Cs3* <Co, indicating that solidication is not completed yet. Solidication actually ends when the average composition of solid equals Co, i.e., at T4.
    Equilibrium solidus
    Co Cs1 Cs 2 Cs * 2 Cs * 3 T3 (end of solidification under equilibrium) T4 (actual end of solidification) T1 (start of solidification) T2

    Effective solidus

    %B

    Non-equilibrium solidification lowers effective melting temperature.

    Coring
    T1 T2 Cs1 L Cs1
    Cs1 Cs 2 Cs * 2 T3 (end of solidification under equilibrium) T4 (actual end of solidification)

    Equilibrium solidus
    Co T1 (start of solidification) T2

    Cs2 T3

    Average solid composition: Cs2*

    Average solid composition: Cs3* T4

    Cs * 3

    Effective solidus

    Average solid composition: Co

    A %B The cored structure: composition segregation, enrichment of high-Tm constituent in the core

    Coring in Eutectic Systems


    According to the lever rule, the weight fraction of the eutectic products can be computed as: Under equilibrium condition: a b c d co L

    Weut

    cb = d b ca = d a
    A

    Under non-equilibrium condition:

    * eut

    * Weut > Weut

    Coring leads to increase of weight fraction of eutectic products

    Constitutional Supercooling
    Co S C CL Co CS T x Tm T S Supercooling window caused by rising Tm, resulting in unstable interface x L A %B L CS CL

    Dendrite Structure of Metals


    A consequence of constitutional supercooling and destabilisation of solid-liquid interface is the formation of dendritic structure, as commonly found in alloy castings. In such structure, gaps between dendrites and between dentitic ngers are regions rich of low-melting temperature phases and impurities. Dendritic branches themselves are often cored, too. This often require post-casting heat treatment to homogenise the structure.

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